Anti-reflection film, liquid composition, liquid composition set, and method for producing anti-reflection film

Abstract

The anti-reflection film (1a) is a film provided on the substrate (3). The antireflection film (1a) is provided with a first layer (11) and a second layer (12) in this order from the front surface side thereof. The first layer 11 has a refractive index nL1 of 1.10 to 1.35 and a thickness tL1 of 80 nm to 150 nm. The second layer (12) has a refractive index (nL2) of 1.30-1.55 and a thickness (tL2) of 25 nm or less.

Description

Technical Field

[0001] The present invention relates to an antireflection film, a liquid composition, a liquid composition set, and a method for producing an antireflection film. Background Art

[0002] Conventionally, there is known a technique for preventing or reducing the reflection of light from the surface of an article.

[0003] For example, Patent Document 1 describes a substrate having a coating formed on the substrate surface, wherein the coating comprises hollow spherical silica particles and a matrix for coating formation. In the silica particles, a cavity is formed inside a shell having pores, and a solvent or gas is contained in the cavity. Since the silica particles have a low refractive index, the coating also has a low refractive index, and the coating has excellent anti-reflection performance.

[0004] Patent Document 2 describes an antireflection film having a hard coating layer, a high refractive index layer and a low refractive index layer on the surface of an organic film from the lower layer side. The high refractive index layer is a synthetic resin film containing fine particles of metal oxides such as ZrO2. The synthetic resin is an ultraviolet or electron beam curable synthetic resin.

[0005] Patent document 3 describes an anti-reflection laminate, which includes a coating film formed by a single coating using a coating composition, wherein the coating composition is dispersed with low refractive index particles and medium to high refractive index particles in a binder resin. As low refractive index particles, silica particles treated with a fluorine-based compound are used. Thus, due to the difference in specific gravity, the low refractive index particles are biased to the upper part to the middle part of the coating film, and the medium to high refractive index particles are biased to the middle part to the lower part.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2001-233611

[0009] Patent Document 2: Japanese Patent Application Publication No. 2001-350001

[0010] Patent Document 3: Japanese Patent Application Publication No. 2007-272132 Summary of the invention

[0011] Problems to be solved by the invention

[0012] The techniques described in Patent Documents 1 to 3 have room for further study from the perspective of antireflection performance. The present invention provides a novel antireflection film that is advantageous from the perspective of antireflection performance.

[0013] Means for solving problems

[0014] The present invention provides an anti-reflection film, which is an anti-reflection film provided on a substrate, wherein:

[0015] The antireflection film includes a first layer and a second layer in order from the surface side of the antireflection film,

[0016] The first layer has a refractive index n of 1.10 to 1.35. L1 and a thickness of 80nm to 150nm,

[0017] The second layer has a refractive index n of 1.30 to 1.55. L2 and thickness below 25nm.

[0018] Effects of the Invention

[0019] The above-mentioned antireflection film is advantageous from the viewpoint of antireflection performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a cross-sectional view showing an example of the antireflection film of the present invention.

[0021] Figure 2 This is a side view showing an example of an optical component including the antireflection film of the present invention.

[0022] Figure 3A This is a cross-sectional view showing another example of the antireflection film of the present invention.

[0023] Figure 3B This is a cross-sectional view showing still another example of the antireflection film of the present invention.

[0024] Figure 3C It is shown Figure 3A A cross-sectional view showing a state of first hollow fine particles in an antireflection film.

[0025] Figure 3D It is shown Figure 3A A cross-sectional view showing a state of first hollow fine particles in an antireflection film.

[0026] Figure 4 This is a cross-sectional view showing still another example of the antireflection film of the present invention.

[0027] Figure 5 This is a graph showing the reflection spectrum of the antireflection film of Example 1.

[0028] Figure 6 This is a graph showing the reflection spectrum of the antireflection film of Example 4.

[0029] Figure 7 This is a graph showing the reflection spectrum of the antireflection film of Example 5.

[0030] Figure 8 This is a graph showing the reflection spectrum of the antireflection film of Example 7.

[0031] Fig. 9 This is a SEM image of a cross section of the antireflection film of Example 1.

[0032] Fig.10 This is a SEM image of a cross section of the antireflection film of Example 5. DETAILED DESCRIPTION

[0033] Hereinafter, embodiments of the present invention will be described with reference to the drawings. It should be noted that the following description is an example of the present invention, and the present invention is not limited to the following embodiments.

[0034] The anti-reflection film is, for example, arranged on the surface of an optical article. Examples of optical articles provided with the anti-reflection film are optical elements such as optical filters, lenses and polarizing elements, various displays, glasses and transparent shields. It is considered that by applying a material having a specified refractive index to an optical article, an anti-reflection film that suppresses the reflection of light from the surface of the optical article is formed. For example, in fields or uses such as windows and structural materials used in optical elements such as lenses and filters, buildings, etc., windshields for automobiles, and shields such as helmets and goggles, the anti-reflection film can play an important role. Through the anti-reflection film, the reflection of light from the surface of these articles or substrates can be suppressed, and the amount of light passing through these articles or substrates can be increased. Here, the anti-reflection film is composed of a single layer or two or more layers with different materials, production conditions, and methods, and is arranged on the surface of an article or substrate in order to prevent or reduce the reflection of light from the surface of an article or substrate.

[0035] For example, the reflectivity of one surface of a transparent dielectric made of glass or resin is usually about 4 to 5%. Therefore, considering the reflection of the surface and the reflection of the back, the overall reflectivity for a plate-shaped transparent dielectric will be 8 to 10%. For example, an imaging device such as a camera usually has an optical system including two or more lenses made of transparent dielectrics such as glass and resin. The amount of reflection from the lens surface in the optical system is very large, and the amount of light reaching the light-receiving surface of the imaging element such as CCD and CMOS is greatly reduced. Furthermore, the reflected light from the surface of these lenses made of transparent dielectrics such as glass or resin is repeatedly reflected or refracted by the internal structure of the imaging device or other lens surfaces and reaches the light-receiving surface of the imaging element, which may cause undesirable phenomena such as ghosting or light spots. Therefore, it is important to form an anti-reflection film on the surface of an object or substrate that performs functions such as transmission or refraction of light to suppress surface reflection.

[0036] like Figure 1As shown, the anti-reflection film 1a is a film provided on a substrate 3. The anti-reflection film 1a includes a first layer 11 and a second layer 12 in order from the surface side. The substrate 3 may be an article used to transmit light in a desired wavelength range. The substrate 3 may be a transparent dielectric. The second layer 12 is arranged between the first layer 11 and the substrate 3 in the thickness direction of the anti-reflection film 1a. The first layer 11 has a refractive index n of 1.10 to 1.35. L1 and a thickness of 80nm to 150nm L1 The second layer 12 has a refractive index n of 1.30 to 1.55. L2 and thickness t below 25nm L2 According to such a configuration, the antireflection film 1a can exhibit high antireflection performance. Refractive index n L1 and refractive index n L2 It is the refractive index at the D line (wavelength 589.3nm).

[0037] In the antireflection film 1a, for example, in a reflection spectrum showing the wavelength and the reflectivity with respect to the wavelength when light with a wavelength of 300 nm to 1200 nm is incident at an incident angle of 5°, the minimum reflectivity r in the range of wavelengths of 300 nm to 1200 nm is min 300-1200 It can be 1% or less. min 300-1200 It is preferably 0.5% or less, and more preferably 0.2% or less. Unless otherwise specified, the reflectance of an antireflection film or the like is the reflectance obtained from a reflection spectrum when light with a wavelength of 300 nm to 1200 nm is incident at an incident angle of 5°.

[0038] In the antireflection film 1a, the minimum reflectivity r in the wavelength range of 400nm to 800nm min 400-800 It is not limited to a specific value. min 400-800 For example, it is 0.5% or less. In this case, the antireflection film 1a can more easily exhibit high antireflection performance. min 400-800 It is preferably 0.2% or less.

[0039] In the antireflection film 1a, the reflectance is within the range of 2.5% or less in the wavelength range of 300nm to 1200nm. range / 2.5 Not limited to a specific value. Range λ range / 2.5 For example, it is 400 nm or more. Thus, the anti-reflection film 1a can more easily exert high anti-reflection performance. Range λ range / 2.5It may be 450 nm or more, or 500 nm or more. Hereinafter, unless otherwise specified, the wavelength and wavelength range corresponding to a predetermined reflectance are also the wavelengths obtained from the reflection spectrum.

[0040] In the antireflection film 1a, the reflectance is within the range of 1.0% or less in the wavelength range of 300nm to 1200nm. range / 1.0 Not limited to a specific value. Range λ range / 1.0 For example, it is 250 nm or more. As a result, the anti-reflection film 1a can more easily exert high anti-reflection performance. Range λ range / 1.0 It may be 300 nm or more, 350 nm or more, or 400 nm or more.

[0041] like Figure 1 As shown, in the antireflection film 1a, the second layer 12 is formed, for example, in direct contact with the surface of the substrate 3. Another layer or another film may be disposed between the second layer 12 and the surface of the substrate 3 in the thickness direction of the antireflection film 1a.

[0042] In the antireflection film 1a, for example, n L1 <n L2 In this case, the anti-reflection film 1a is more likely to exhibit high anti-reflection performance.

[0043] The thickness of the second layer t L2 It is preferably 15 nm or less, more preferably 10 nm or less, and still more preferably 5 nm or less. Thus, the antireflection film 1a can more easily exhibit high antireflection performance.

[0044] like Figure 1 As shown, in the anti-reflection film 1a, the first layer 11 and the second layer 12 form a first multilayer structure 10. The thickness t of the first multilayer structure 10 is LL For example, it is 100 nm to 160 nm. In this case, the antireflection film 1a can more easily exert high antireflection performance. The D line (wavelength λ D : The substantial or representative refractive index n at 589.3 nm) LD and thickness t LL Satisfy t LL =λ D / (4n LD ) condition, the reflectivity at line D is the smallest. Therefore, from the perspective of high anti-reflection performance, the thickness t LL The thickness is advantageously 100 nm to 160 nm.

[0045] In the antireflection film 1a, the thickness t LL and any wavelength λ X [nm] can satisfy λ X / 6≤tLL ≤λ X In this case, in the antireflection film 1a, in addition to the wavelength λ X In addition to the fact that the reflectivity at the wavelengths where the reflectivity is below a predetermined value can be increased, this is advantageous. X For example, it may be a specific wavelength included in the wavelength range of 400 nm to 800 nm, it may be a D line (wavelength 589.3 nm), it may be a wavelength representing the wavelength range of the light used, it may be a central wavelength of the wavelength range of the light used, or it may be the most important wavelength in the wavelength range of the light used. The most important wavelength in the wavelength range of the light used may be a wavelength corresponding to the lowest reflectivity in a prescribed wavelength range.

[0046] The refractive index of the substrate is n sb When the refractive index of the anti-reflection film is n1, the optical thickness of the anti-reflection film is considered to be adjusted to 1 / 4 of the specified wavelength λ. sb -n1 2 The smaller the absolute value of the value is, the easier it is for the reflectivity to become smaller at the wavelength λ corresponding to the refractive index. Therefore, from the perspective of reducing the reflectivity, it is sometimes preferred that the actual refractive index of the anti-reflection film is low. In the case where a low refractive index is required for the anti-reflection film, it is advantageous for the anti-reflection film to contain hollow particles.

[0047] like Figure 1 As shown, the first multilayer structure 10 includes, for example, first hollow particles 21 and a first binder 31. The first binder 31 bonds the first hollow particles 21. According to such a structure, the first layer 11 and the second layer 12 are easy to have a desired refractive index and a desired thickness, and the anti-reflection film 1a is more likely to exert a high anti-reflection performance. In addition, by making the first multilayer structure 10 include the first hollow particles 21, as described later, in addition to being able to reduce the actual refractive index of the anti-reflection film 1a, it is also expected that the mechanical strength such as peeling resistance and abrasion resistance and the weather resistance such as moisture resistance can be improved. In this specification, the microparticles are particles having an average particle size of less than 1 μm.

[0048] Even if the material constituting the shell of the first hollow particle 21 has a predetermined refractive index, the hollow portion 21a inside it can be considered to be filled with air. Therefore, by including the first hollow particle 21 in the first multilayer structure 10, the actual refractive index is likely to be lowered. The first hollow particle 21 has, for example, a hollow balloon-type structure. The refractive index of the first hollow particle 21 is, for example, 1.10 to 1.40, preferably 1.15 to 1.40, and more preferably 1.17 to 1.35. It should be noted that the refractive index of the first hollow particle 21 is not the refractive index of the material constituting the shell of the first hollow particle 21, but the actual refractive index of the first hollow particle 21 that also includes the effect of the hollow portion 21a. The refractive index of the first hollow particle at a specific wavelength is sometimes also widely known, or representative or average values ​​such as the size of the approximate sphere of the hollow particle, the material of the shell of the hollow particle, and the thickness can be obtained, for example, by using the Bruggemann effective medium approximation method to obtain.

[0049] The material constituting the shell of the first hollow particle 21 is not limited to a specific material. The material may be an inorganic material, an organic material, or an organic-inorganic hybrid material. Examples of inorganic materials constituting the shell of the first hollow particle 21 are silicon oxide (silicon dioxide) and magnesium fluoride. Examples of organic materials constituting the shell of the first hollow particle 21 are polystyrene and polyethylene. These materials may be used alone, or two or more materials may be mixed and used. From the perspective of the ease of manufacture of the hollow particles, the main component of the shell of the first hollow particle 21 is preferably silicon oxide. In this specification, the main component is the component that contains the most on a mass basis.

[0050] The shape of the first hollow fine particles 21 is not limited to a specific shape. The first hollow fine particles 21 may be substantially spherical, may be irregular in shape, or may be a form in which specific shapes are linked in a chain.

[0051] The average particle size D of the first hollow fine particles 21 p It is not limited to a specific value. Average particle size D p For example, the average particle size D is 5 to 200 nm. p When the average particle size D is 5 nm or more, the manufacturing cost of the first hollow fine particle 21 can be easily reduced. In addition, it is possible to prevent the refractive index from being insufficiently reduced due to the small volume of the hollow portion 21a. pThe diameter of the first hollow particle 21 is less than 200nm, and even if light is incident on the first hollow particle 21, scattering is suppressed, which easily prevents the haze of the anti-reflection film 1a from becoming high. The confirmation and measurement of the size and shape of the particles can be carried out, for example, by observation using a scanning electron microscope (SEM). As the average particle size of the particles, a 100,000-fold SEM image of a cross section at right angles to the main surface of an article or the like formed with a film containing particles can be obtained, and the particles can be determined. After the shape of the particles is approximated to a circle, its diameter is measured, and the arithmetic mean of the diameters of the particles contained in a predetermined area, for example, a 500nm square range containing all the layers constituting the anti-reflection film is used. This method is simple when calculating the average particle size of the particles contained in the cured film or layer. It should be noted that in the SEM image, when the shape of the particles is approximated to a circle, the circle of the minimum diameter of the area containing each particle can also be determined as an approximate circle.

[0052] Average particle size D p It is preferably 10 to 100 nm, more preferably 30 to 80 nm.

[0053] The outer shell of the first hollow fine particles 21 may be crystalline, polycrystalline, or amorphous.

[0054] The thickness t of the shell of the first hollow particle 21 S It is not limited to a specific value. Thickness t S For example, it is 1 to 50 nm. S When the thickness t is 1 nm or more, the mechanical strength of the outer shell is likely to be high, and the hollow structure of the first hollow fine particle 21 is likely to be maintained in a desired state. S The thickness t of the outer shell of the hollow fine particle is 50 nm or less, so that the first hollow fine particle 21 can be easily manufactured. S The effective medium approximation using the Bruggemann equation can be used to estimate the volume from the relationship between the substantial refractive index of the hollow fine particles, the volume of the approximate sphere of the hollow fine particles, the volume of the hollow portion, and the like.

[0055] In the first hollow particle 21, the shell thickness t S Relative to the average particle size D p Ratio t S / D p Not limited to a specific value. S / D p For example, 1 / 50 to 1 / 5.

[0056] The first hollow microparticle 21 can also be a hollow microparticle whose surface has been modified. For example, microparticles formed by pre-reacting a compound having a metal component, an alkyl group and an alkoxy group in one molecule or a hydrolyzate of the compound can be used. In this case, the compound can contain reactive functional groups such as amino, epoxy, methacryloyl and vinyl. In addition, as such a compound, a compound called a coupling agent can also be used. The coupling agent contains components such as Si, Ti or Al. In this specification, Si is treated as a metal component.

[0057] In the manufacture of the anti-reflection film 1a, the particles used for the first hollow particles 21 can be provided in the form of a powder or in the form of a dispersion of particles. The dispersion of particles can be in a colloidal state. For example, colloidal silica as a colloidal dispersion of particles of silicon oxide can be used. By using a dispersion of particles, the dispersion state of the particles is stably maintained, the haze of the anti-reflection film 1a is easily reduced, and the anti-reflection film 1a is easily transparent. The dispersion medium of the dispersion can be alcohols, ketones, esters, ethers, aromatic hydrocarbons, or amides. Examples of alcohols are methanol, ethanol, isopropanol, butanol, and octanol. Examples of ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters are ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Ethers are ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, and diethylene glycol monobutyl ether. Aromatic hydrocarbons include benzene, toluene and xylene. Examples of amides include dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Among them, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, toluene and xylene are preferred as dispersion media.

[0058] The first hollow fine particles 21 may be Thrulya 1110 (silicon oxide, average particle size (nominal) about 50 nm, solid content concentration about 20 mass %) manufactured by JGC Catalysts & Chemicals Co., Ltd., or Thrulya 4110 (silicon oxide, average particle size (nominal): 50 nm to 60 nm, solid content concentration: about 20 to 25 mass %) manufactured by the same company. These are hollow fine particles with silicon oxide as the main component of the shell.

[0059] The anti-reflection film 1a contains a binder such as the first binder 31. The binder is used to bond the particles contained in the anti-reflection film 1a to each other, and to bond the particles to the substrate or base layer. The binder is originally a material for bonding materials such as particles, pigments, and substrates within a layer, but a component that is cured to form a uniform structure within a layer that does not contain pigments or particles is also treated as a binder in this specification.

[0060] The material of the binder contained in the anti-reflection film 1a is not limited to a specific material. The binder can be, for example, a compound or composition whose precursor is liquid, which is cured by heating or irradiation with electromagnetic waves such as light. If the precursor of the binder is liquid, in the manufacture of the anti-reflection film 1a, the preparation of the precursor of the anti-reflection film 1a is easy, and the addition of particles, the dispersion of particles, the colloidization of particles, or the dissolution of particles are easy.

[0061] The precursor of the binder can be, for example, a monomer or oligomer having polymerizable unsaturated groups such as acryloyl, vinyl, and allyl in the molecule. The precursor of the binder can be a compound having more than one polymerizable unsaturated group in one molecule. The precursor of the binder is not limited to a specific compound. Examples of precursors of the binder are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, neopentyl glycol mono (meth)acrylate, trimethylolpropane di (meth)acrylate, trimethylolethane di (meth)acrylate, pentaerythritol tri (meth)acrylate, and dipentaerythritol penta (meth)acrylate. The precursor of the binder can be a compound obtained by the addition reaction of glycidyl-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, and (meth)acrylate glycidyl with (meth)acrylic acid. The precursor of the binder may be a compound containing a polymerizable functional group, or may be a precursor of a silicone resin, an epoxy resin, a phenoxy resin, a novolac resin, a silicone acrylate resin, a melamine resin, a phenolic resin, a polyimide resin, or a polyurethane resin.

[0062] The binder precursor may include a metal alkoxide having a metal component and an alkoxy group represented by the following formula (A) or a hydrolyzate thereof. x and R y is a functional group containing at least a carbon atom, M is a metal atom, and n and m refer to the number of functional groups substantially contained in one molecule.

[0063] R x m M(OR y ) n Formula (A)

[0064] The metal component is selected from the group consisting of Si, Ti, Nb, Zr and Al. The binder precursor may preferably include an alkoxysilane having Si and an alkoxy group represented by the following formula (B), a hydrolyzate thereof, or a polysilane obtained by polymerizing the hydrolyzate thereof. 1 and R 2 are identical or different functional groups containing carbon atoms and hydrogen atoms, and n is an integer of 1-4.

[0065] R1 4-n Si(OR 2 ) n Formula (B)

[0066] Such alkoxysilanes are hydrolyzed in the presence of water to generate silanol groups (-Si-OH), which then undergo polycondensation to generate siloxane bonds (-O-Si-O-) between multiple molecules. As a result, the molecular weight increases to generate a polymer, making it easier to obtain a binder containing silica or silsesquioxane. Silica is generated by the reaction of a tetrafunctional alkoxysilane satisfying n=4 in formula (B). Silsesquioxane is generated by the reaction of a trifunctional alkoxysilane satisfying n=3 in formula (B).

[0067] Silicon dioxide is the main component of glass. Conventional glass requires a process of melting silica sand at a very high temperature. However, the solidification of the composition containing silicon dioxide using alkoxysilane can be achieved at low temperatures, which is advantageous from this aspect. In addition, the binder using alkoxysilane as a part of the raw material can contain silicon dioxide, etc., so it is also advantageous from the aspect of durability. In addition, for the binder using alkoxysilane as a part of the raw material, for example, even in the inner package of microparticles with silicon oxides such as silicon dioxide as the main component, from aspects such as affinity with microparticles or hydrogen bond formation with microparticles, it is also easy to have the desired characteristics, and it can be expected that the bonding strength of microparticles will increase. In addition, the refractive index difference between the binder and the microparticles is easy to become smaller, and the transparency of the layer or film containing the binder and the microparticles is easy to become higher.

[0068] The alkoxysilane contained in the precursor of the binder is not limited to a specific alkoxysilane. Examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra(isopropoxy)silane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, methyltriisopropoxysilane, ethyltriisopropoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, and dimethyl Diethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi(isopropoxy)silane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldi(isopropoxy)silane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylpropyldi(isopropoxy)silane, methoxysilane, ethoxysilane, methylmethoxysilane, methylethoxysilane, dimethylmethoxysilane, dimethylethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, Trimethyl (isopropoxy) silane, triethyl methoxy silane, triethyl ethoxy silane, triethyl (isopropoxy) silane, tripropyl methoxy silane, tripropyl ethoxy silane, tripropyl (isopropoxy) silane, methyl diethyl methoxy silane, methyl diethyl ethoxy silane, methyl diethyl (isopropoxy) silane, methyl dipropyl methoxy silane, methyl dipropyl ethoxy silane, methyl dipropyl (isopropoxy) silane, ethyl dimethyl ethoxy silane, ethyl dimethyl (isopropoxy) silane, ethyl dipropyl methoxy silane, ethyldipropylethoxysilane, ethyldipropyl(isopropoxy)silane, propyldimethylmethoxysilane, propyldimethylethoxysilane, propyldimethyl(isopropoxy)silane, propyldiethylmethoxysilane, propyldiethylethoxysilane, propyldiethyl(isopropoxy)silane, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(trimethoxysilyl)ethane, bis(triethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,3-Bis(triethoxysilyl)propane, hexamethoxydisiloxane, hexaethoxydisiloxane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tetraacetoxysilane, tetrakis(trichloroacetoxy)silane, tetrakis(trifluoroacetoxy)silane, triacetoxysilane, tris(trichloroacetoxy)silane, tris(trifluoroacetoxy)silane, methyltriacetoxysilane, methyltris(trichloroacetoxy)silane, methyltris(trifluoroacetoxy)silane, methyldiacetoxysilane, methylbis(trichloroacetoxy)silane, methylbis(trifluoroacetoxy)silane, dimethylbis(trichloroacetoxy)silane, dimethylbis (Trifluoroacetoxy)silane, methylacetoxysilane, methyl(trichloroacetoxy)silane, methyl(trifluoroacetoxy)silane, dimethylacetoxysilane, dimethyl(trichloroacetoxy)silane, dimethyl(trifluoroacetoxy)silane, trimethylacetoxysilane, trimethyl(trichloroacetoxy)silane, trimethyl(trifluoroacetoxy)silane, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, methyldichlorosilane, methyldibromosilane, methyldifluorosilane, dimethyldichlorosilane, dimethyldibromosilane, dimethyldifluorosilane, methylchlorosilane, methylbromosilane, methylfluorosilane, dimethylchlorosilane, dimethylbromosilane, dimethylfluorosilane, trimethylchlorosilane, trimethylbromosilane and trimethylfluorosilane. The binder or the precursor of the binder may be a hydrolyzate of these alkoxysilanes having a silanol group, or a compound obtained by polymerizing the hydrolyzate of these alkoxysilanes through a siloxane bond. The binder or the precursor of the binder may contain two or more alkoxysilanes, hydrolyzates of two or more alkoxysilanes, or polymers of hydrolyzates of two or more alkoxysilanes.

[0069] The alkoxysilane contained in the precursor of the binder may have reactive functional groups or polymerizable unsaturated groups such as acryloyl and epoxy groups in addition to alkoxy groups in one molecule. Examples of such alkoxysilanes are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriacetoxysilane, 3-acryloxypropyltris(trichloroacetoxy)silane, 3-acryloxypropyltris(trifluoroacetoxy)silane, 3-methacryloxypropyltriacetoxysilane, 3-methacryloxypropyltris(trichloroacetoxy)silane, 3-Methacryloxypropyltris(trifluoroacetoxy)silane, 3-glycidoxypropyltriacetoxysilane, 3-glycidoxypropyltris(trichloroacetoxy)silane, 3-glycidoxypropyltris(trifluoroacetoxy)silane, 3-acryloxypropyltrichlorosilane, 3-acryloxypropyltribromosilane, 3-acryloxypropyltrifluorosilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropyltribromosilane, 3-methacryloxypropyltrifluorosilane, 3-glycidoxypropyltrichlorosilane, 3-glycidoxypropyltribromosilane and 3-glycidoxypropyltrifluorosilane.

[0070] The first binder 31 includes, for example, at least one selected from the group consisting of alkoxysilane, a hydrolyzate of alkoxysilane, and a polymer of a hydrolyzate of alkoxysilane. Thus, the antireflection film 1 a can more easily exhibit high antireflection performance.

[0071] The second layer 12, for example, includes a first binder 31 present near the surface of the substrate 3 and a portion of the shell of the first hollow particle 21 present near the surface of the substrate 3. A portion of the first hollow particle 21 present near the surface of the substrate 3 can be in contact with the surface of the substrate 3. Therefore, the second layer 12 is almost filled with solids and contains almost no hollow parts and voids where air exists. For example, when the main component of the shell of the first hollow particle 21 is silicon oxide, and the first binder 31 contains a hydrolyzate of alkoxysilane or a polymer of the hydrolyzate, the second layer 12 can be composed of a material with silicon oxide as the main component. In this case, the refractive index of the second layer 12 is close to the refractive index of silicon oxide or a modified product of silicon oxide. On the other hand, the first layer 11 includes the shell of the first hollow particle 21, the hollow part 21a of the first hollow particle 21, and the voids between the first hollow particles 21. In this way, air with a refractive index of about 1 exists in the first layer 11. Therefore, the first layer 11 and the second layer 12 are easy to have the desired refractive index and the desired thickness, and are easy to satisfy n L1 <n L2In the first layer 11, the larger the volume occupied by air, the higher the refractive index n of the first layer 11. L1 The easier it is to become smaller, the easier it is to satisfy n L1 <n L2 conditions.

[0072] The thickness of the second layer 12 is, for example, smaller than the average particle diameter D of the first hollow fine particles 21. p In addition, the thickness of the second layer 12 may also be less than the thickness of the outer shell t S .

[0073] As long as the substrate 3 is provided with an anti-reflection film 1a on its surface, it is not limited to a specific substrate. The optical properties of the anti-reflection film 1a can also take into account the optical properties of the substrate 3. The substrate 3 is, for example, a substrate for an image display device such as a display. The substrate 3 can be an optical element such as an optical filter, a lens, and a diffraction element. The optical filter causes the incident light to produce a prescribed physical change, and can play a function of transmission, reflection, absorption, diffusion, or a combination thereof. The lens produces focusing or divergence through the refraction of light. The diffraction element can diffract light and play a prescribed function by having a concave-convex on its surface or inside.

[0074] like Figure 1 As shown, the substrate 3 is, for example, in the form of a flat plate. The substrate 3 may have a curved surface on all or part of its surface, or may have a smooth surface including projections and depressions. For example, when the substrate 3 is a lens, the surface of the substrate 3 may include a curved surface. In addition, the substrate 3 may also be a substrate for a windshield of a helmet and a display screen of a head-mounted display. In this case, the entire substrate 3 is gently curved. When the substrate 3 is a diffraction element, it may have projections and depressions on its surface that are the size of the wavelength of the light to be diffracted or a size close to the wavelength.

[0075] Figure 2 1 is a side view showing an example of an optical component including a substrate 3 and an anti-reflection film 1a. Figure 2 As shown, the substrate 3 can be a lens such as a convex lens.

[0076] The material of the substrate 3 is not limited to a specific material. The substrate 3 is, for example, a material that can function as an optical article. The substrate 3 has, for example, high transparency and includes glass or resin. Glass is not limited to a specific glass. Examples of glass are soda-lime glass, borosilicate glass, aluminosilicate glass, (synthetic) quartz, lead glass, barium glass, phosphate glass, fluorophosphate glass, and lanthanum glass. The glass may be glass made by a sol-gel method. In this case, a structure of the wavelength size of light is easily formed. The raw material of the glass used in the sol-gel method is a compound having a metal and an alkoxy group.

[0077] The resin contained in the substrate 3 is not limited to a specific resin. Examples of the resin include acrylic (methacrylic) resins, styrene resins, polycarbonate resins, polyolefin resins, epoxy resins, polyethylene resins, polypropylene resins, ABS resins, polyamide resins, polyacetal resins, and polyethylene terephthalate resins.

[0078] The refractive index n of the substrate 3 at line D SB For example, it may be 1.20 to 2.50, may be 1.30 to 2.30, or may be 1.35 to 2.00.

[0079] The antireflection film 1 a or a layer included in the antireflection film 1 a can be produced by, for example, curing a predetermined liquid composition.

[0080] The liquid composition comprises a precursor of a binder and particles as required. The liquid composition may further comprise an organic polymer, examples of which may be polyethers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, or polyisocyanate compounds. Thus, when the liquid composition is cured, these organic polymers act as crosslinking agents, and can improve mechanical properties such as hardness and scratch resistance, light resistance or weather resistance of the anti-reflection film 1a.

[0081] A polymerization initiator may be added to the liquid composition and is selected from known polymerization initiators such as thermal radical generators, photoradical generators, thermal acid generators, and photoacid generators, depending on the reaction form of the polymerizable functional group or polymerizable monomer.

[0082] In the case where the precursor of the binder partially contains alkoxysilane or its hydrolyzate, the liquid composition may contain water for promoting hydrolysis, an acid (acid catalyst) or a base (base catalyst) acting as a catalyst. Examples of acids (acid catalysts) are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, formic acid and acetic acid, and examples of base catalysts are ammonia, trialkylamine, sodium hydroxide, potassium hydroxide, choline and tetraalkylammonium hydroxide. Among them, formic acid and acetic acid are organic acids that can dissolve alkoxysilane. In addition, these acids have the characteristics of being substantially halogen-free, having a small acid dissociation constant (pKa) (pKa = 3.7 (formic acid), 4.7 (acetic acid)) and being a strong acid, and are preferred as acid catalysts. In the case of using acetic acid and formic acid as acid catalysts, silanol groups are generated even when there is little or no water in the system, so a polysilane structure can be formed without hydrolysis. From this aspect, formic acid and acetic acid are also preferably used. In addition, formic acid has a relatively simple structure among organic acids, so it is easy to exert the desired properties as an acid catalyst.

[0083] The liquid composition can be prepared, for example, by adding a catalyst dropwise to a liquid containing alkoxysilane while stirring the liquid, thereby preventing a large amount of catalyst compound from being added at once and causing the reaction to proceed too quickly, and making it less likely that the reaction will vary.

[0084] The liquid composition may include a solvent. The solvent also helps to disperse particles, for example, and the liquid composition is easy to have a desired viscosity during the manufacture of the anti-reflection film 1a. In addition, it is easy to adjust the coating operation of the liquid composition or the quality of the coating film to the desired level. The compounds of metal alkoxides such as alkoxysilane as the raw materials of the binder 31 are sometimes difficult to dissolve just after mixing with the water required for hydrolysis. Therefore, the liquid composition may include an organic solvent that is compatible with both metal alkoxides and water. The solvent included in the liquid composition is not limited to a specific solvent. The solvent included in the liquid composition may be an alcohol, a ketone, an ester, an ether, an aromatic hydrocarbon, or an amide. Examples of alcohols are methanol, ethanol, isopropanol, butanol, octanol, 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol. Examples of ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Examples of esters are ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Examples of ethers are ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether and diethylene glycol monobutyl ether. Examples of aromatic hydrocarbons are benzene, toluene and xylene. Examples of amides are dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Organic acids such as acetic acid and formic acid can also be used as solvents in the preparation of liquid compositions. Among them, it is preferred to use at least one selected from the group consisting of methanol, isopropanol, butanol, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, toluene and xylene as a solvent. These solvents can be used alone, or two or more solvents can be mixed and used.

[0085] In order to prevent the microparticles from agglomerating with each other, the liquid composition may contain a hydrophilic and hydrophobic compound such as a surfactant and a silane coupling agent.

[0086] The liquid composition can be prepared by selecting the types of microparticles, binder precursor, solvent, catalyst and the above-mentioned compounds, adjusting the composition ratio of each component by a known method and conditions, and reacting some of the compounds as needed, and mixing them.

[0087] In the liquid composition as the precursor of the first multilayer structure 10 of the antireflection film 1a, the mass ratio of the solid content of the first hollow particles 21 to the mass ratio of the solid content of the liquid composition is not limited to a specific value. The ratio is, for example, 80% to 99.5%. According to such a structure, the first layer 11 and the second layer 12 are easy to have a desired refractive index and a desired thickness. The precursor of the first binder 31 in the liquid composition, for example, only needs to play the role of bonding the first hollow particles 21 to each other or bonding the first hollow particles 21 to the surface of the substrate 3. The precursor of the first binder 31 contained in excess of the amount required for the bonding of the first hollow particles moves toward the surface of the substrate 3 during the manufacture of the antireflection film 1a and solidifies, and can form a part of the second layer 12. As described above, the second layer 12 is filled with solids such as a part of the shell of the hollow particles 21 and the first binder 31, and is a layer having a relatively high refractive index in the first multilayer structure 10. The first binder 31, for example, contains a hydrolyzate of alkoxysilane or a polymer thereof.

[0088] The ratio of the mass of the solid content of the first hollow fine particles 21 to the mass of the solid content of the liquid composition as the precursor of the first multilayer structure 10 is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more.

[0089] The liquid composition as the precursor of the first multilayer structure 10, for example, includes at least one selected from the group consisting of alkoxysilane and the hydrolyzate of alkoxysilane as the precursor of the first adhesive 31. In this case, the alkoxysilane includes a tetrafunctional alkoxysilane and a trifunctional alkoxysilane, and the ratio of the amount of the tetrafunctional alkoxysilane to the amount of the trifunctional alkoxysilane is not limited to a specific value. The ratio is, for example, 1 / 9 to 9. In this case, the first layer 11 and the second layer 12 are easy to have a desired refractive index and a desired thickness. In addition, the first multilayer structure 10 is easy to have a desired mechanical strength and high transparency.

[0090] The anti-reflection film 1a can be manufactured, for example, by applying a liquid composition containing the first hollow particles 21 and at least one selected from the group consisting of alkoxysilane and a hydrolyzate of alkoxysilane onto the substrate 3 and curing the liquid composition. The mass ratio of the first hollow particles 21 to the liquid composition is 80% to 99.5%. The anti-reflection film 1a includes the first layer 11 and the second layer 12 separately. According to such a method, the anti-reflection film 1a having the first layer 11 and the second layer 12 can be manufactured relatively easily using a single liquid composition.

[0091] The method of coating the liquid composition as a precursor of the anti-reflection film 1a along the substrate 3 is not limited to a specific method. Examples of the method include roller coating, spray coating, spin coating, coating using a dispenser, coating using an inkjet, screen printing, and coating using dipping. The conditions of the coating method are adjusted according to the thickness required for the coating. For example, in the case of coating using dipping, when the viscosity of the liquid composition is set to η [Pa·second] and the speed during lifting is set to v [m / second], the thickness of the coating, for example, the thickness t of the first multilayer structure 10 LL With η j ×v k Here, the conditions of j = 0.5 to 0.6 and k = 0.5 to 0.7 hold. In addition, in the coating by spin coating, when the rotation angular velocity is set to ω [radian / second], the thickness of the coating film is proportional to η 1 / 3 / ω 2 / 3 Proportional.

[0092] The method of curing the liquid composition is not limited to a specific method. The curing of the liquid composition can be carried out by a method of drying the coating or polymerizing the precursor of the binder by heating. In this case, heating can also include the following situation, even in an environment maintained at about room temperature, especially in an environment without artificial heating means, such as standing still in the interior of a container, a thermostatic bath or a table, the liquid composition is cured by drying or reaction. The curing of the liquid composition can also be carried out by polymerizing the precursor of the binder by irradiation with electromagnetic waves such as visible light, ultraviolet rays and microwaves.

[0093] A coating refers to a liquid composition applied to a surface of a substrate, etc., regardless of whether the coating is a sol or a gel. Solidification includes: the molecular weight of the binder component contained in the liquid composition increases through polymerization of the compounds contained in the liquid composition, and the liquid composition becomes gelled; the solvent or liquid byproduct contained in the liquid composition is removed by evaporation, etc., and the liquid composition is dried and gelled; and solidification occurs through a mechanism associated with mixing of the liquid composition; or a mixed mechanism thereof. Furthermore, solidification includes: a reaction or drying of the liquid composition proceeds to produce a solid containing an organic compound and an inorganic compound; the organic matter in the liquid composition is removed to obtain a substantially inorganic solid; and a mixture of these solids is obtained.

[0094] The surface of the substrate 3 to which the liquid composition is applied may be subjected to various cleaning or surface treatments before the liquid composition is applied. The cleaning of the surface of the substrate 3 is not limited to a specific method. The cleaning of the surface of the substrate 3 may be cleaning with an organic solvent or water, or may be acid or alkali cleaning accompanied by immersion in an acid or alkali solution. Examples of surface treatments on the surface of the substrate 3 are mechanical treatments such as sandblasting and grinding, corona discharge treatment, flame treatment, UV-O3 cleaning, and plasma irradiation treatment. It is expected that the following advantages will be brought about by these cleanings or surface treatments: improvement of the wettability of the liquid composition on the surface of the substrate 3; or generation of hydroxyl groups, etc., which are easily bonded to the compounds contained in the liquid composition; etc.

[0095] In the manufacture of the anti-reflection film 1a, it is preferred that the gelation of the liquid composition can occur relatively slowly after the coating of the liquid composition is formed along the surface of the substrate 3. In this case, the fluidity of the precursor of the microparticle or binder can be maintained to a certain extent before the gelation of the liquid composition. Therefore, for the layer constituting the anti-reflection film 1a, it is more preferred to dry or react the liquid composition by heating to solidify it, rather than quickly solidifying the liquid composition by irradiation with electromagnetic waves, etc. The heating temperature of the liquid composition is, for example, 600°C or less, preferably 400°C or less, more preferably 300°C or less, and further preferably 250°C or less. The heating time of the liquid composition also depends on the heating temperature, for example, 2 hours or less, preferably 1 hour or less, more preferably 30 minutes or less, and further preferably 15 minutes or less. Such heating conditions can be determined by considering the properties required for the anti-reflection film 1a and the heat-resistant temperature of the substrate 3. For example, there is a trade-off: if the heating temperature of the liquid composition is high, the resulting film is dense and hardened, but cracks are easily generated and the brittleness is obvious.

[0096] As described above, the refractive index n of the second layer 12 is L2 is 1.30 to 1.55, and the thickness t of the second layer 12 L2 In addition, the refractive index n of the first layer 11 is L1 is 1.10 to 1.35, the thickness t of the first layer 11 L1 The physical parameters of each layer of the antireflection film 1a can also be measured or calculated as follows. The average particle size D of the hollow fine particles 21 is measured from a SEM image of a cross section of the antireflection film 1a. p and the thickness t of the first multilayer structure 10 composed of the first layer 11 and the second layer 12 LL. In addition, the reflection spectrum of the anti-reflection film 1a is measured using a spectrophotometer or the like. Next, using appropriate simulation software, the values ​​of the parameters corresponding to the refractive index and thickness of the first layer 11 and the second layer 12 when each layer is assumed to be filled with a uniform medium are changed successively, and the reflection spectrum is calculated. Then fitting is performed. In fitting, for example, the refractive index and thickness of each layer are determined in such a way that a specific error parameter between the measured reflection spectrum measured by a spectrophotometer or the like and the calculated reflection spectrum is minimized. The main function of the anti-reflection film 1a is to prevent reflection from the surface of a transparent optical article or substrate. Therefore, the reflectivity may become low in the measured reflection spectrum of the anti-reflection film 1a. Therefore, for example, the anti-reflection film 1a can be formed on the surface of a silicon wafer with a known refractive index dispersion in the same method and conditions as when the anti-reflection film 1a is formed on the surface of the substrate 3, and the measured reflection spectrum of the anti-reflection film 1a formed on the surface of the silicon wafer is used for fitting. In the calculation of the reflection spectrum, it can be assumed that the thickness of the second layer 12 is t L2 Less than the thickness t of the outer shell of the hollow particle 21 S In the calculation of the reflection spectrum, the thickness t of the second layer 12 L2 The value of the corresponding parameter can be uniquely determined as a specific thickness determined in consideration of the amount of solid components in the liquid composition, for example, 4 nm or 2 nm.

[0097] The specific error parameter between the measured reflection spectrum and the calculated reflection spectrum used for fitting is not limited to a specific parameter. Examples of the error parameter are correlation coefficient, root mean square value (rms value), mean square value (MS value) and mean absolute difference (MA value). When calculating the parameters related to the anti-reflection film 1a, the integral value of the absolute difference at each wavelength in the measured reflection spectrum and the calculated reflection spectrum (IA value: Integrate of Absolute) can also be used. When calculating the measured reflection spectrum and the calculated reflection spectrum for each unit wavelength (for example, 1 nm), the sum of the absolute differences of the reflectivity at each wavelength can also be used instead of the IA value. The IA value is determined according to the following formula (1). In formula (1), r m is the measured reflectivity at wavelength λ, r s is the reflectivity at wavelength λ obtained by calculation. m -r s | is the absolute value of the reflectivity difference, and λ1 and λ2 represent the integration range or the range to be summed. The sum of the absolute differences in reflectivity is determined according to the following formula (2).

[0098] [Number 1]

[0099]

[0100] [Number 2]

[0101]

[0102] In the anti-reflection film 1a, the sum of the absolute differences of the IA value or the reflectivity is preferably 20% or less, more preferably 18% or less, and further preferably 15% or less. The range for obtaining the sum of the absolute differences of the IA value or the reflectivity can be, for example, within the range of 300nm to 1200nm. Considering the accuracy of the spectrophotometer for measurement, the range can be within the range of 350nm to 900nm, or within the range of 400nm to 850nm.

[0103] The anti-reflection film 1a can be changed from various viewpoints. For example, the anti-reflection film 1a can be changed to Figure 3A or Figure 3B The anti-reflection film 1b is shown. The anti-reflection film 1b is constructed in the same manner as the anti-reflection film 1a except for the parts specifically described. The components of the anti-reflection film 1b that are the same as or correspond to the components of the anti-reflection film 1a are marked with the same symbols, and detailed descriptions are omitted. The above description of the anti-reflection film 1a is also applicable to the anti-reflection film 1b as long as there is no technical contradiction.

[0104] like Figure 3A or Figure 3B As shown, the antireflection film 1b further includes a third layer 13 disposed between the second layer 12 and the substrate 3 in the thickness direction of the antireflection film 1b. The third layer 13 has a refractive index n of 1.35 to 2.25. L3 and a thickness of 60nm to 200nm M3 According to such a structure, the anti-reflection film 1b can easily exert high anti-reflection performance. According to the anti-reflection film 1b, the reflectivity at a specific wavelength, such as the design center wavelength, can easily become low, and the wavelength band where the reflectivity is kept below a specific value, i.e., the low reflection band, can easily become large. Refractive index n L3 It is the value at D line (589.3nm).

[0105] Refractive index n L3 It may be 1.40 to 1.85. In the antireflection film 1b, it is preferred that n L1 <n L3 <n L2 In this case, the anti-reflection film 1b is more likely to exert high anti-reflection performance. In the anti-reflection film 1b, n L1 <n L2 ≤n L3 Conditions. Thickness t M3 It can be 70nm to 180nm.

[0106] In the antireflection film 1b, the minimum reflectivity r in the wavelength range of 300nm to 1200nm is min(2)For example, it is 1% or less, more preferably 0.5% or less, and further preferably 0.2% or less. In the reflection spectrum of the antireflection film 1b, the wavelength range λ where the reflectivity is 1% or less within the wavelength range of 300nm to 1200nm is range / 1.0 For example, it is 250 nm or more.

[0107] The material constituting the third layer 13 is not limited to a specific material as long as the third layer 13 has the above-mentioned refractive index and thickness. The third layer 13 may also be a layer containing dielectrics such as metal oxides and metal fluorides. The third layer 13 may be, for example, a dielectric film made by physical methods such as vacuum evaporation, sputtering and ion plating (hereinafter referred to as "physical evaporation method"), or a so-called dielectric multilayer film in which two or more dielectrics are stacked. The material of the dielectric is not limited to a specific material. Examples of dielectric materials are SiO2, MgF2, TiO2, Ta2O3, AlF3, CaF2, Al2O3, ZrO2, WO3, CeO2, ITO, ATO and mixtures thereof. Such a dielectric layer can be made by a known method using a physical evaporation method, etc.

[0108] The third layer 13 may be a layer obtained by drying and reacting a coating film formed by applying a curable liquid composition along the surface of the substrate 3 and curing the coating film. Figure 3B As shown in FIG. 1 , the curable liquid composition as the precursor of the third layer 13 may include fine particles 33 and may include a second binder 32 for bonding the fine particles 33 to each other. When the third layer 13 is produced using such a curable liquid composition, a vapor deposition device or the like required by a physical vapor deposition method is not required, and the manufacturing cost of the anti-reflection film 1b is easily reduced. When the third layer 13 is produced using a curable liquid composition, as shown in FIG. Figure 3A As shown, the third layer 13 may also not contain the particles 33 but only contain the second binder 32 .

[0109] In the case where the third layer 13 is made by curing a curable liquid composition, the refractive index of the particles 33 contained in the third layer 13 is, for example, 1.25 to 2.75. The material of the particles 33 contained in the third layer 13 is not limited to a specific material. The particles 33 can be, for example, hollow or solid particles containing metal oxides or metal fluorides such as SiO2, MgF2, TiO2, Ta2O3, AlF3, CaF2, Al2O3, ZrO2, WO3, CeO2, indium tin oxide (ITO) and antimony tin oxide (ATO). The particles 33 can include two or more particles selected from these particles. The particles 33 can also be particles made of resin. The particles 33 can include, for example, solid particles with polymethyl methacrylate, polyethylene, polystyrene, benzoguanamine (melamine) or silicone as the main component, or can include two or more particles selected from them.

[0110] The third layer 13 may include the following layers (i) or (ii), or (i) and (ii).

[0111] (i) A layer comprising a dielectric film, wherein the dielectric film comprises one or more oxides selected from the group consisting of SiO2, MgF2, TiO2, Ta2O3, AlF3, CaF2, Al2O3, ZrO2, WO3, CeO2, indium tin oxide, and antimony tin oxide.

[0112] (ii) A layer comprising oxide particles and a binder for bonding the oxide particles, wherein the oxide particles are composed of one or more materials selected from the group consisting of SiO2, TiO2, ZrO2, CeO2, indium tin oxide and antimony tin oxide.

[0113] The third layer 13 is disposed closer to the substrate 3 than the first layer 11 and the second layer 12 in the thickness direction of the antireflection film 1b, so from the perspective of improving the antireflection performance, it is sometimes appropriate for the third layer 13 to have a higher refractive index. In this case, for example, the microparticles 33 contained in the third layer 13 are preferably solid microparticles. Considering the refractive index required for the third layer 13, the microparticles 33 may include metal oxides such as titanium oxide (TiO2; refractive index = 2.50 to 2.75; specific gravity 4.1 to 4.4), zirconium oxide (ZrO2; refractive index = 2.00 to 2.20; specific gravity 5.5), cerium oxide (CeO2; refractive index = 2.00 to 2.30; specific gravity 7.0), ATO (refractive index = 1.70 to 1.85; specific gravity 6.6), or ITO (refractive index = 1.90 to 2.20; specific gravity 7.1), etc. The microparticles 33 may also include silicon oxide (SiO2; refractive index = 1.41 to 1.48). From the perspective of anti-reflection performance, the microparticles 33 may also be hollow microparticles if appropriate.

[0114] The average particle size of the microparticles 33 is not limited to a specific value. The average particle size is, for example, 5 nm to 200 nm. By making the average particle size of the microparticles 33 greater than 5 nm, the manufacturing cost of the microparticles 33 can be easily reduced. By making the average particle size of the microparticles 33 less than 200 nm, it is easy to prevent the haze of the anti-reflection film 1b from increasing due to scattering of incident light. The average particle size of the microparticles 33 is preferably 10 to 100 nm, more preferably 30 to 80 nm. The average particle size of the microparticles 33 contained in the third layer 13 can be adjusted by comparing it with the average particle size D of the first hollow microparticles 21. p The measurement method is the same as the measurement method.

[0115] The content of the microparticles 33 in the solid component of the third layer 13 is not limited to a specific value. Its content is, for example, 0% to 75% on a mass basis. As a result, the third layer 13 easily has a desired refractive index. As described above, the third layer 13 may not contain microparticles. Even in the case where the refractive index of the third layer 13 is required to be relatively high, the third layer 13 may not contain microparticles as long as the anti-reflection film 1b has a specified anti-reflection performance. In this case, the third layer 13 contains, for example, a binder 32 as a main component. In this case, in the preparation of the liquid composition as a precursor of the third layer 13, the supply, adjustment and mixing of microparticles are not required, and the manufacturing cost of the anti-reflection film 1b is easily reduced.

[0116] Figure 3C and Figure 3D It is shown Figure 3A 2 is a cross-sectional view of the state of the first hollow particles 21 in the anti-reflection film shown. Figure 3C and Figure 3D As shown, in the anti-reflection film 1b, a part of the first hollow particles 21 included in the first layer 11 and the second layer 12 may be present at the boundary surface of the third layer 13 and the third layer 13 at a position far from the substrate 3. For example, it is considered that after the third layer 13 is formed, as the coating film of the liquid composition as the precursor of the first multilayer structure 10 is cured, a part of the hollow particles 21 included in the first layer 11 and the second layer 12 is buried in the third layer 13, so that a part of the first hollow particles 21 exists at the boundary surface of the third layer 13 at a position far from the substrate 3. Figure 3CThe portion surrounded by the double-dashed line in the figure represents the portion where the hollow particles 21 are buried in the third layer 13. From the perspective of achieving such a state in which a portion of the first hollow particles 21 is buried in the third layer 13, it is considered that the components and composition of the third layer 13 are preferably similar to those of the multilayer structure 10. In particular, if the first binder 31 and the second binder 32 are similar, and the precursors of the first binder 31 and the second binder 32 are also similar, then in the manufacture of the anti-reflection film 1b, mixing of the precursor of the first binder 31 and the precursor of the second binder 32 is likely to occur. For example, if there are pores in the third layer 13, the liquid composition applied to the surface of the third layer 13 at a position farther from the substrate 3 can penetrate in a manner that fills the pores. As a result, the second binder 32 also contains the same type of compound as a part of the compound contained in the first binder 31, and the first binder 31 and the second binder 32 can be homogenized. As a result, it is believed that the surface of the third layer 13 is softened, and a portion of the first hollow particles 21 is embedded in the third layer 13, and exists on the boundary surface of the third layer 13 at a position far from the substrate 3. It should be noted that the similarity between the first binder 31 and the second binder 32 means that, in addition to the same composition and composition of the two, the types of compounds contained in the binders such as alkoxysilane are similar, specifically, the trifunctional alkoxysilane or tetrafunctional alkoxysilane contained in the two is the same type of alkoxysilane. It is known that pores can be formed during the curing of a liquid composition containing alkoxysilane, and it is believed that a portion of the uncured liquid composition easily penetrates into the portion having such pores.

[0117] like Figure 3C As shown, within the range of the cross-sectional area of ​​the antireflection film 1b, the first hollow particles 21 existing at the boundary of the third layer 13 far from the substrate 3 are identified, and the number of the first hollow particles 21 can be counted. Figure 3D As shown, for each first hollow particle 21 existing at the boundary, the proportion of the portion existing on the third layer 13 side in the entire first hollow particle 21 can be calculated. A 100,000-fold SEM image of the cross section of the anti-reflection film 1b is obtained to identify the first layer 11, the second layer 12, and the third layer 13. On this basis, a 500 nm square object cross section is specified in such a way as to include all layers in the thickness direction. The first hollow particle 21 contained in the object cross section and existing at a boundary farther from the substrate 3 in the third layer 13 is determined, and the first hollow particle 21 is approximated by a circle. The number N of first hollow particles 21 having portions belonging to the second layer 12 and the third layer 13 contained in the object cross section is measured and calculated. M1 , the area S of the partial circle (a shape where a part of the circle is missing) included in the region on the third layer 13 side MWith respect to the total area S of the approximate circle of the first hollow fine particle 21 having the portion belonging to the second layer 12 and the third layer 13 L Ratio S M / S L In the anti-reflection film 1b, the number N M1 For example, it is 1 to 5, preferably 3 to 5. M / S L For example, it is 5% to 50%. If the first hollow particles 21 are present at the boundary of the third layer 13 at a position far from the substrate 3, the first hollow particles 21 are bonded by both the binder of the third layer 13 and the binder of the layer in contact with the third layer 13, so the bonding strength between the third layer 13 and the layer in contact with the boundary of the third layer 13 at a position far from the substrate 3 is likely to be high.

[0118] The particles 33 included in the third layer 13 are not limited to specific particles. The particles 33 may be titanium oxide particles such as TTO-51 and TTO-55 series manufactured by Ishihara Sangyo Co., Ltd., JMT-150B, JMT-150AO, JMT-150ANO and MTY-700BS manufactured by TAYCA, STT-65C-S and STT-30EHJ manufactured by Titan Kogyo, Ltd., and OPTOLAKE series manufactured by JGC Catalysts & Chemicals Co., Ltd. The particles 33 may also be niobium oxide particles such as Nb-G6000, Nb-G6100 and Nb-G6600 manufactured by Taki Chemical Co., Ltd., and niobium oxide manufactured by Mitsui Mining & Smelting Co., Ltd. The particles 33 may also be zirconium oxide particles such as ZIRCOSTAR manufactured by Nippon Shokubai Co., Ltd. and HXU-110JC manufactured by Sumitomo Osaka Cement Co., Ltd. The microparticles 33 may also be silicon oxide microparticles such as the QSG series manufactured by Shin-Etsu Chemical, the SNOWTEX series manufactured by Nissan Chemical, and the Thrulya series manufactured by JGC Catalysts & Chemicals. The microparticles 33 may also be magnesium fluoride nanoparticles manufactured by Stella Chemifa. The microparticles 33 may also be alumina microparticles such as the 100, 200, and 500 series of alumina sol manufactured by Nissan Chemical, and AS-150T and AS-1501 manufactured by Sumitomo Osaka Cement. The microparticles 33 may also be polyethylene microparticles such as polyethylene microparticles manufactured by COREFRONT and the MIPELON series manufactured by Mitsui Chemicals. The microparticles 33 may also be polystyrene microparticles such as polystyrene microparticles manufactured by COREFRONT and Polybead polystyrene manufactured by TECHNO CHEMICAL. The microparticles 33 may also be ITO microparticles such as the ITO series manufactured by Mitsubishi Materials Electronics, and P-120 and P-130 manufactured by JGC Catalysts & Chemicals. The particles 33 may also be ATO particles such as the TI series manufactured by Mitsubishi Materials Electronics Co., Ltd. As the particles 33, particles other than these may be added, and one type of particle may be used alone, or two or more types of particles may be mixed and used. In addition, if conductive particles such as ITO and ATO are used as the particles 33, the anti-reflection film 1b can play an anti-static function. The particles 33 are selected according to the use and function required for the anti-reflection film 1b, and are appropriately combined.

[0119] When the third layer 13 is produced by curing the curable liquid composition, the second binder 32 contained in the third layer 13 is not limited to a specific binder. The second binder 32 can also be selected in consideration of the conditions described in the anti-reflection film 1a regarding the binder. The second binder 32 can include at least one selected from the group consisting of alkoxysilane, a hydrolyzate of alkoxysilane, and a polymer of a hydrolyzate of alkoxysilane.

[0120] The liquid composition as the precursor of the third layer 13 may further contain a cross-linking agent, a polymerization initiator, a leveling agent, a surfactant, a silane coupling agent, and the like as needed, in addition to the precursors of the fine particles 33 and the second binder 32 .

[0121] When the third layer 13 is formed by curing the curable liquid composition, it is not necessary to form the third layer 13 in a state of being separated into two layers during the curing of the coating film of a single type of liquid composition, as in the formation of the first multilayer structure 10 including the first layer 11 and the second layer 12. The optical parameters such as the refractive index can also be roughly uniform throughout the third layer 3.

[0122] The antireflection film 1b can be produced, for example, by a method including the following steps (Ib), (IIb), and (IIIb). The antireflection film 1b includes a first layer and a second layer separated in order from the surface of the antireflection film 1b.

[0123] (Ib) A third layer 13 including a dielectric is formed on the substrate 3.

[0124] (IIb) Applying the first liquid composition including the first hollow fine particles 21 and at least one selected from the group consisting of alkoxysilane and a hydrolyzate of alkoxysilane to the surface of the third layer 13 .

[0125] (IIIb) curing the first liquid composition.

[0126] In (Ib), the third layer 13 can be obtained by coating the second liquid composition of the precursor comprising the second binder 32 on the substrate 3 and solidifying the second liquid composition. In this case, the method for coating the second liquid composition on the substrate 3 is not limited to a specific method. Examples of the method include roller coating, spray coating, spin coating, coating using a dispenser, coating using inkjet, screen printing, and coating using dipping. In addition, in each coating method, the conditions of each method can be set according to the thickness required for the second coating film.

[0127] The method of curing the liquid composition is not limited to a specific method. The curing of the liquid composition can be carried out by a method of drying the coating or polymerizing the precursor of the binder by heating. In this case, heating can also include the following situation, even in an environment maintained at about room temperature, especially in an environment without artificial heating means, such as standing still in the interior of a container, a thermostatic bath or a table, the liquid composition is cured by drying or reaction. The curing of the liquid composition can also be carried out by polymerizing the precursor of the binder by irradiation with electromagnetic waves such as visible light, ultraviolet rays and microwaves.

[0128] The surface of the substrate 3 to which the liquid composition is applied may be subjected to various cleaning or surface treatments before the liquid composition is applied. The cleaning of the surface of the substrate 3 is not limited to a specific method. The cleaning of the surface of the substrate 3 may be cleaning with an organic solvent or water, or may be acid or alkali cleaning accompanied by immersion in an acid or alkali solution. Examples of surface treatments on the surface of the substrate 3 are mechanical treatments such as sandblasting and grinding, corona discharge treatment, flame treatment, UV-O3 cleaning, and plasma irradiation treatment. It is expected that the following advantages will be brought about by these cleanings or surface treatments: improvement of the wettability of the liquid composition on the surface of the substrate 3; or generation of hydroxyl groups, etc., which are easily bonded to the compounds contained in the liquid composition; etc.

[0129] In the manufacture of the anti-reflection film 1b, it is preferred that the gelation of the liquid composition occurs relatively gently after the coating of the liquid composition is formed. In this case, the fluidity of the precursor of the microparticle or binder can be maintained to a certain extent before the gelation of the liquid composition. Therefore, the layer constituting the anti-reflection film 1b is preferably solidified by drying or reacting the liquid composition by heating. The heating temperature of the liquid composition is, for example, below 600°C, preferably below 400°C, more preferably below 300°C, and further preferably below 250°C. The heating time of the liquid composition also depends on the heating temperature, for example, below 2 hours, preferably below 1 hour, more preferably below 30 minutes, and further preferably below 15 minutes. Such heating conditions can be determined by considering the properties required for the anti-reflection film 1b and the heat-resistant temperature of the substrate 3. For example, there is the following trade-off: if the heating temperature of the liquid composition is high, the resulting film is dense and hardened, but cracks are easily generated and the brittleness is obvious.

[0130] The calculation of the parameters of the anti-reflection film 1b can be performed in the same manner as the calculation of the parameters of the anti-reflection film 1a. For example, an anti-reflection film 1b produced on the surface of the substrate 3 or the like and an anti-reflection film produced on the surface of a silicon wafer by the same method and conditions as the anti-reflection film 1b are obtained. The SEM image of the cross section is obtained, the thickness of each layer is measured, each particle contained in each layer is determined, the average particle size, the number N M1 and S M / S L Furthermore, the reflection spectrum of the anti-reflection film 1b is measured, and the reflection spectrum is calculated by taking the refractive index and thickness of each layer as variables, and the refractive index and thickness of each layer are determined in such a way that the error parameter with the measured reflection spectrum is minimized within the allowable range. In this way, the parameters of each layer of the anti-reflection film 1b can be calculated. The error parameter is the same as that described for the anti-reflection film 1a.

[0131] The anti-reflection film 1a may be changed to, for example, Figure 4The anti-reflection film 1c is shown. The anti-reflection film 1c is constructed in the same manner as the anti-reflection film 1a except for the parts specially described. The components of the anti-reflection film 1c that are the same as or correspond to the components of the anti-reflection film 1a are marked with the same symbols, and the detailed description is omitted. The above description of the anti-reflection films 1a and 1b is also applicable to the anti-reflection film 1c as long as there is no technical contradiction.

[0132] like Figure 4 As shown, the anti-reflection film 1c further includes a third layer 13 and a fourth layer 14. The third layer 13 is disposed between the second layer 12 and the substrate 3 in the thickness direction of the anti-reflection film 1c. The fourth layer 14 is disposed between the third layer 13 and the substrate 3 in the thickness direction of the anti-reflection film 1c. The third layer 13 has a refractive index n of 1.30 to 2.25. L3 and a thickness of 60nm to 200nm M3 The fourth layer 14 has a refractive index n of 1.30 to 1.55. L4 and thickness t below 25nm M4 . Refractive index n L3 and n L4 is the value at the D line (589.3nm). According to such a configuration, the anti-reflection film 1c is easy to exert high anti-reflection performance. In the anti-reflection film 1c, for example, the reflectivity at a specific wavelength (design center wavelength) is easy to decrease. The wavelength region where the reflectivity is maintained below a specific value, i.e., the low reflection band, is easy to become larger.

[0133] In the antireflection film 1c, the minimum reflectivity r in the wavelength range of 300nm to 1200nm is min(2) For example, it is 1% or less, preferably 0.5% or less, and more preferably 0.2% or less. In the reflection spectrum of the antireflection film 1c within a wavelength range of 300nm to 1200nm, the wavelength range λ where the reflectance is 1% or less is range / 1.0 For example, it is 250 nm or more.

[0134] Refractive index n L3 Preferably, it is 1.40 to 2.00. Thickness t M3 Preferably, it is 80nm to 160nm. Refractive index n L4 Preferably, it is 1.35 to 1.50. Thickness t M4 Preferably, it is 20 nm or less.

[0135] For example, in the antireflection film 1c, n L3 <n L4 Thus, the anti-reflection film 1c is more likely to exert high anti-reflection performance. In the anti-reflection film 1c, it is preferred to satisfy n L1 <n L2 and n L3 <n L4 conditions.

[0136] like Figure 4 As shown, in the anti-reflection film 1c, the first layer 11 and the second layer 12 form a first multilayer structure 10. In addition, the third layer 13 and the fourth layer 14 form a second multilayer structure 20. The first multilayer structure 10 includes first hollow particles 21 and a first binder 31 for bonding the first hollow particles 21. The second multilayer structure 20 includes second hollow particles 22 and a second binder 32 for bonding the second hollow particles 22. According to such a configuration, the anti-reflection film 1c is more likely to exhibit high anti-reflection performance.

[0137] In the antireflection film 1c, the difference between the refractive index of the first adhesive 31 and the refractive index of the second adhesive 32 is not limited to a specific value. The difference is, for example, 0.01 or less. With such a configuration, the antireflection film 1c can more easily exhibit high antireflection performance.

[0138] like Figure 4 As shown, the second layer 12 includes, for example, a first portion 12a and a second portion 12b. The first portion 12a is a layered portion disposed on the first layer 11 side of the second layer 12. The second portion 12b is a layered portion disposed on the third layer 13 side of the second layer 12.

[0139] The anti-reflection film 1c can be manufactured using, for example, a liquid composition group as a precursor of the anti-reflection film 1c. The liquid composition group includes a first liquid composition and a second liquid composition. The first liquid composition, for example, includes a precursor of the first hollow particles 21 and the first binder 31. By solidifying the first liquid composition, the first layer 11 and the first portion 12a of the second layer 12 can be formed. The second liquid composition includes a precursor of the second hollow particles 22 and the second binder 32. By solidifying the second liquid composition, the second portion 12b of the second layer 12, the third layer 13, and the fourth layer 14 can be formed.

[0140] The antireflection film 1c can be produced, for example, through the steps including the following (Ic) and (IIc).

[0141] (Ic) The second portion 12b of the second layer 12, the third layer 13, and the fourth layer 14 are formed by at least one selected from the group consisting of drying the second coating film obtained by applying the second liquid composition along the surface of the substrate 3 and reacting the second coating film.

[0142] (IIc) by selecting at least one of the group consisting of drying the first coating film obtained by applying the above-mentioned first liquid composition on the second part 12b of the second layer 12 and the reaction of the first coating film, the first part 12a of the second layer 12 and the first layer 11 are separately formed, and the first part 12a and the second part 12b are combined to form the second layer 12.

[0143] The antireflection film 1c can be produced, for example, by a method including the following steps (Id), (IId), (IIId), and (IVd).

[0144] (Id) Applying a second liquid composition including second fine particles containing an oxide and at least one selected from the group consisting of alkoxysilane and a hydrolyzate of alkoxysilane onto the substrate 3 .

[0145] (IId) solidifying the second liquid composition.

[0146] (IIId) Applying the first liquid composition including the first hollow fine particles 21 and at least one selected from the group consisting of alkoxysilane and a hydrolyzate of alkoxysilane to the surface of the cured product of the second liquid composition.

[0147] (IVd) solidifying the first liquid composition.

[0148] The antireflection film 1c includes, for example, a first layer 11, a second layer 12, a third layer 13, and a fourth layer 14 in order from the surface of the antireflection film 1c. The second layer 12 includes a portion of the shell of the first hollow fine particles 21, a portion of the polymer of the hydrolyzate of alkoxysilane, and a portion of the second fine particles.

[0149] In (Id), the mass ratio of the second fine particles to the second liquid composition is, for example, 5% to 75%. In (IIId), the mass ratio of the first hollow fine particles 21 to the first liquid composition is, for example, 80% to 99.5%.

[0150] The precursors of the first binder 31 and the second binder 32 may both contain a predetermined alkoxysilane, and the first layer 11, the second layer 12, the third layer 13, and the fourth layer 14 may each contain at least one of a hydrolyzate of alkoxysilane and a polymer of a hydrolyzate of alkoxysilane. The predetermined alkoxysilane is, for example, an alkoxysilane selected from the group consisting of a hydrolyzate of alkoxysilane and a polymer of a hydrolyzate of alkoxysilane, and the difference between the refractive index of the first binder 31 and the refractive index of the second binder 32 can be 0.01 or less, and is at least one precursor. For example, in the predetermined alkoxysilane, the mass ratio of trifunctional alkoxysilane to tetrafunctional alkoxysilane is 1 / 4 to 4. According to such a configuration, in the step (IIc), the first portion 12a and the second portion 12b are combined to form a substantially identical layer, and the first layer 11, the second layer 12, the third layer 13, and the fourth layer 14 are sequentially arranged toward the substrate 3.

[0151] like Figure 4As shown, in the anti-reflection film 1c, the fourth layer 14 closest to the substrate 3 among the first layer 11, the second layer 12, the third layer 13 and the fourth layer 14 contains a material constituting the shell of the hollow particles 22. For example, in the case where the first binder 31 and the second binder 32 contain at least one selected from the group consisting of hydrolyzates of alkoxysilane and polymers of hydrolyzates of alkoxysilane, and the first hollow particles 21 and the second hollow particles 22 are composed of compounds with silicon oxide as the main component, the fourth layer 14 can be filled with the compound with silicon oxide as the main component. For example, in the case where the shell of the second hollow particle 22 composed of a compound with silicon oxide as the main component contains a hydrolyzate of alkoxysilane or a polymer of the hydrolyzate as the main component, the fourth layer 14 has almost no hollow parts and gaps filled with air, but is filled with alkoxysilane, hydrolyzate of alkoxysilane and polymer of hydrolyzate of alkoxysilane. Therefore, the refractive index n of the fourth layer 14 is L4 The refractive index of the hollow fine particles 22 can be a value that is not significantly different from that of silicon oxide or its modified product. L4 And t M4 If the thickness is 25 nm or less, materials other than silicon oxide may be included.

[0152] The third layer 13 can be arranged at a position farther from the substrate 3 than the fourth layer 14. Figure 4 As shown, the third layer 13 is a layer including the shell and the hollow part of the second hollow particle 22. There is air with a refractive index of about 1 in the hollow part of the second hollow particle 22 and in the gaps between the second hollow particles 22. Therefore, the greater the proportion of such an area containing air in the third layer 13, the greater the refractive index n of the third layer. L3The easier it is to reduce. Before applying the first liquid composition, the second liquid composition is applied, and in the process of forming the second portion 12b, the third layer 13 and the fourth layer 14, a part of the second hollow particles 22 can be present at the interface of the second portion 12b at a position farther from the substrate 3. The second portion 12b, like the fourth layer 14, can contain, for example, in addition to the second binder 32, a compound constituting the shell of the second hollow particle 22 containing, for example, silicon oxide as a main component. When the layer constituting the anti-reflection film 1c contains alkoxysilane, a hydrolyzate of alkoxysilane, or a polymer of a hydrolyzate of alkoxysilane, and the second hollow particle 22 is composed of a compound containing silicon oxide as a main component, the second portion 12b can be filled with the compound containing silicon oxide as a main component. When the hollow fine particles composed of a compound whose main component is silicon oxide are formed of a compound whose main component is a hydrolyzate of alkoxysilane or a polymer of a hydrolyzate of alkoxysilane, the second portion 12b is not likely to include a hollow portion and a void, and is filled with alkoxysilane, a hydrolyzate of alkoxysilane, or a polymer of a hydrolyzate of alkoxysilane. Therefore, in the anti-reflection film 1c, the refractive index of the second portion 12b can be a value that is not significantly different from the refractive index of silicon oxide or a modified product of silicon oxide.

[0153] In the step (IIc), the first portion 12a of the second layer 12 is formed separately from the first layer 11. The formation of the first layer 11 and the first portion 12a in the anti-reflection film 1c corresponds to the formation of the first layer 11 and the second layer 12 in the anti-reflection film 1a, respectively. Therefore, with regard to the formation of the first layer 11 and the first portion 12a in the anti-reflection film 1c, the description of "the second layer 12" of the anti-reflection film 1a can be replaced with "the first portion 12a" for reference.

[0154] In the anti-reflection film 1c, the first hollow particles 21 and the second hollow particles 22 may preferably be particles of the same type having an outer shell containing silicon oxide as a main component. The first hollow particles 21 and the second hollow particles 22 may also be particles of the same or different types containing components other than silicon oxide as a main component as long as the refractive index and thickness of each layer are within a specified range. As described above, the first binder 31 and the second binder 32 are preferably selected so that the difference in refractive index between the two is 0.01 or less.

[0155] The ratio M of the mass of the solid content of the first hollow fine particles 21 to the mass of the solid content of the first liquid composition L For example, the ratio M of the mass of the solid content of the second hollow fine particles 22 to the mass of the solid content of the second liquid composition is greater than H According to such a configuration, the antireflection film 1c can more easily exhibit high antireflection performance.

[0156] In the liquid composition set as a precursor of the antireflection film 1c, the ratio of M L and M H Preferably, 0.05≤M H / M L ≤0.85, more preferably 0.2≤M H / M L ≤0.7. As a result, the antireflection film 1c can more easily exhibit high antireflection performance.

[0157] M L For example, it is 80% to 99.5%, preferably 85% to 99.5%, more preferably 90% to 99.5%, and even more preferably 95% to 99%. H For example, it is 5% to 70%, preferably 10% to 50%.

[0158] The method of applying the first liquid composition and the second liquid composition as the precursor of the anti-reflection film 1c is not limited to a specific method. Examples of the method include roller coating, spray coating, spin coating, coating using a dispenser, coating using an inkjet, screen printing, and coating using dipping. The conditions of the coating method are adjusted according to the thickness required for the coating film.

[0159] The method of solidification of the first liquid composition and the second liquid composition is not limited to a specific method. The solidification of these liquid compositions can be carried out according to the method of drying the coating or producing the polymerization of the precursor of the binder by heating. In this case, heating can also include the following situations, even in an environment maintained at about room temperature, especially in an environment without artificial heating means, such as standing still in the interior of a container, a thermostatic bath or a table, the liquid composition is also solidified with drying or reaction. The solidification of the liquid composition can also be carried out by polymerizing the precursor of the binder by irradiation with electromagnetic waves such as visible light, ultraviolet rays and microwaves.

[0160] The surface of the substrate 3 to which the second liquid composition is applied may be subjected to various cleaning or surface treatments before the second liquid composition is applied. The cleaning of the surface of the substrate 3 is not limited to a specific method. The cleaning of the surface of the substrate 3 may be cleaning with an organic solvent or water, or may be acid or alkali cleaning accompanied by immersion in an acid or alkali solution. Examples of surface treatments on the surface of the substrate 3 are mechanical treatments such as sandblasting and grinding, corona discharge treatment, flame treatment, UV-O3 cleaning, and plasma irradiation treatment. It is expected that the following advantages will be brought about by these cleanings or surface treatments: improvement of the wettability of the liquid composition on the surface of the substrate 3; or generation of hydroxyl groups, etc., which are easily bonded to the compounds contained in the liquid composition; etc.

[0161] In the manufacture of the anti-reflection film 1c, it is preferred that after forming a coating of the liquid composition along the surface of the substrate 3, the gelation of the liquid composition occurs relatively gently. In this case, the fluidity of the precursor of the microparticles or the binder can be maintained to a certain extent before the gelation of the liquid composition. Therefore, the layer constituting the anti-reflection film 1c is preferably solidified by drying or reacting the liquid composition by heating. The heating temperature of the liquid composition is, for example, below 600°C, preferably below 400°C, more preferably below 300°C, and further preferably below 250°C. The heating time of the liquid composition also depends on the heating temperature, for example, below 2 hours, preferably below 1 hour, more preferably below 30 minutes, and further preferably below 15 minutes. Such heating conditions can be determined by considering the properties required for the anti-reflection film 1c and the heat-resistant temperature of the substrate 3. For example, there is the following trade-off: if the heating temperature of the liquid composition is high, the resulting film is dense and hardened, but cracks are easily generated and the brittleness is obvious.

[0162] The calculation of the parameters of the anti-reflection film 1c can be performed in the same manner as the calculation of the parameters of the anti-reflection film 1a. For example, an anti-reflection film 1c produced on the surface of the substrate 3 or the like and an anti-reflection film produced on the surface of a silicon wafer by the same method and conditions as the anti-reflection film 1c are obtained. The SEM image of the cross section is obtained, the thickness of each layer is measured, each particle contained in each layer is determined, the average particle size, the number N M1 and S M / S L Furthermore, the reflection spectrum of the anti-reflection film 1c is measured, and the refractive index and thickness of each layer are used as variables to calculate the reflection spectrum, and the refractive index and thickness of each layer are determined in such a way that the error parameter with the measured reflection spectrum is minimized within the allowable range. In this way, the parameters of each layer of the anti-reflection film 1c can be calculated. The error parameter is the same as that described for the anti-reflection film 1a.

[0163] The anti-reflection films 1a, 1b and 1c can be changed from various viewpoints. For example, the anti-reflection film can have k layers. In this case, the first layer 11, the second layer 12, the third layer 13 (omitted) and the kth layer can be arranged in sequence toward the substrate 3. k is, for example, an integer greater than 5.

[0164] Example

[0165] The present invention will be described in more detail by way of examples. It should be noted that the present invention is not limited to the following examples.

[0166] <Binder Precursor A1>

[0167] 44.6 g of tetraethoxysilane (TEOS) manufactured by Tokyo Chemical Industry Co., Ltd., 16.4 g of methyltriethoxysilane (MTES) manufactured by the same company, and 37.9 g of a 0.3 mass % formic acid aqueous solution manufactured by Kishida Chemical Co., Ltd. were mixed and stirred to obtain a binder precursor A1 as a transparent liquid composition. The mass ratio of TEOS to MTES in the binder precursor A1 was 7:3.

[0168] <Binder Precursor A2>

[0169] 33.6 g of TEOS, 28.6 g of MTES, and 37.9 g of a 0.3 mass % formic acid aqueous solution manufactured by Kishida Chemical Co., Ltd. were mixed and stirred to obtain a binder precursor A2 as a transparent liquid composition. The mass ratio of TEOS to MTES in the binder precursor A2 was 5:5.

[0170] <Binder Precursor A3>

[0171] 19.0 g of TEOS, 38.0 g of MTES, and 37.9 g of a 0.3 mass % formic acid aqueous solution manufactured by Kishida Chemical Co., Ltd. were mixed and stirred to obtain a binder precursor A3 as a transparent liquid composition. The mass ratio of TEOS to MTES in the binder precursor A3 was 3:7.

[0172] <Binder Precursor A4>

[0173] 5.8 g of TEOS, 45.2 g of MTES, and 37.9 g of a 0.3 mass % formic acid aqueous solution manufactured by Kishida Chemical Co., Ltd. were mixed and stirred to obtain a binder precursor A4 as a transparent liquid composition. The mass ratio of TEOS to MTES in the binder precursor A4 was 1:9.

[0174] <Binder Precursor A5>

[0175] 19.2 g of TEOS, 36.1 g of n-propyltrimethoxysilane (n-PTMS), and 37.9 g of a 0.3 mass % formic acid aqueous solution manufactured by Kishida Chemical Co., Ltd. were mixed and stirred to obtain a binder precursor A5 as a transparent liquid composition. The mass ratio of TEOS to n-PTMS in the binder precursor A5 was 3:7.

[0176] <Liquid composition B1>

[0177] 0.14 g of the binder precursor A1 was added to 86.0 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and Thrulya 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd. (a dispersion of approximately 20% by mass of roughly spherical hollow silica particles, 70% by mass of 2-propanol and 10% by mass of methanol, with an average particle size (nominal) of 60 nm and a refractive index of 1.25) was added so that the solid content of the particles was 99% relative to the total solid content, and the mixture was mixed and stirred to prepare a liquid composition B1 containing hollow particles and a binder precursor.

[0178] <Liquid Composition B2>

[0179] 2.7 g of the binder precursor A2 was added to 82.3 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and Thrulya 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd. was added so that the solid content mass of the microparticles was 95% relative to the total solid content mass, and the mixture was mixed and stirred to prepare a liquid composition B2 containing hollow microparticles and a binder precursor.

[0180] <Liquid composition B3>

[0181] 4.4 g of the binder precursor A3 was added to 81.9 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and Thrulya 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd. was added so that the solid content mass of the microparticles was 90% of the total solid content mass, and the mixture was mixed and stirred to prepare a liquid composition B3 containing hollow microparticles and a binder precursor.

[0182] <Liquid composition B4>

[0183] 3.7 g of the binder precursor A4 was added to 81.3 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and Thrulya 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd. was added so that the solid content mass of the microparticles was 90% of the total solid content mass, and the mixture was mixed and stirred to prepare a liquid composition B4 containing hollow microparticles and a binder precursor.

[0184] <Liquid Composition B5>

[0185] 4.4 g of the binder precursor A5 was added to 81.9 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and Thrulya 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd. was added so that the solid content mass of the microparticles was 95% relative to the total solid content mass, and the mixture was mixed and stirred to prepare a liquid composition B5 containing hollow microparticles and a binder precursor.

[0186] <Liquid Composition B6>

[0187] 14.8 g of the binder precursor A1 was added to 82.8 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and the mixture was mixed and stirred to prepare a liquid composition B6 containing a binder precursor.

[0188] <Liquid Composition B7>

[0189] 14.8 g of the binder precursor A1 was added to 82.8 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and Thrulya 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd. was added so that the solid content mass of the microparticles was 13.1% relative to the total solid content mass, and the mixture was mixed and stirred to prepare a liquid composition B7 containing microparticles and a binder precursor.

[0190] <Liquid composition B8>

[0191] 14.8 g of the binder precursor A3 was added to 82.8 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and Thrulya 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd. was added so that the solid content mass of the microparticles was 10.0% relative to the total solid content mass, and the mixture was mixed and stirred to prepare a liquid composition B8 containing microparticles and a binder precursor.

[0192] <Liquid composition B9>

[0193] 15.7 g of binder precursor A1 was added to 71.4 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and titanium oxide particles OPTOLAKE (average particle size 8 to 12 nm (nominal); solvent: methanol, etc.) manufactured by JGC Catalysts & Chemicals Co., Ltd. were added in a manner that the solid content mass of the particles was 54.2% relative to the total solid content mass, and the mixture was mixed and stirred to prepare a liquid composition B9 containing the particles and the binder precursor.

[0194] <Liquid composition B10>

[0195] 0.04 g of the binder precursor A1 was added to 86.2 g of a mixed liquid of 1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol, and Thrulya 4110 manufactured by JGC Catalysts & Chemicals Co., Ltd. was added so that the solid content mass of the microparticles was 99.8% relative to the total solid content mass, and the mixture was mixed and stirred to prepare a liquid composition B10 containing hollow microparticles and a binder precursor.

[0196] <Example 1>

[0197] As the substrate, a borosilicate glass material D263 T eco (refractive index n 2.1 mm) manufactured by Corning Incorporated was used. D :1.5230) substrate, the substrate is properly cleaned with an alkaline solution and an organic solvent, and a liquid composition B1 is appropriately dripped on one main surface of the substrate to form a coating film by spin coating. The substrate is a square with a side length of 70 mm when viewed from above. Next, the substrate formed with the coating film is placed in a constant temperature dryer, and after being placed at 30°C for 30 minutes, the temperature inside the constant temperature dryer is adjusted to 200°C, and the temperature is maintained at 200°C for 10 minutes. After that, the temperature inside the constant temperature dryer is naturally cooled to room temperature, and the substrate provided with a low refractive index layer is taken out from the constant temperature dryer to prepare the anti-reflection film of Example 1.

[0198] <Example 2>

[0199] As the substrate, a borosilicate glass material D263 T eco (refractive index n 2.1 mm) manufactured by Corning Incorporated was used. D :1.5230) substrate, the substrate is properly cleaned with an alkaline solution and an organic solvent, and a liquid composition B2 is appropriately dripped on one main surface of the substrate to form a coating film by spin coating. Next, the temperature inside the thermostatic bath is pre-adjusted to 200°C, the substrate with the coating film formed is placed in the thermostatic bath, and after 10 minutes, the substrate is taken out of the thermostatic bath, and the substrate is placed in a room at a room temperature of 25°C to cool the substrate, thereby preparing the anti-reflection film of Example 2.

[0200] <Example 3>

[0201] An antireflection film of Example 3 was produced in the same manner as in Example 2 except that the liquid composition B4 was used instead of the liquid composition B2.

[0202] <Example 4>

[0203] As the substrate, a borosilicate glass material D263 T eco (refractive index n 2.1 mm) manufactured by Corning Incorporated was used. D:1.5230) substrate, the substrate is properly cleaned with an alkaline solution and an organic solvent, and a liquid composition B6 is dripped on one main surface of the substrate in an appropriate amount to form a coating film by spin coating. Next, the temperature inside the thermostatic bath is pre-adjusted to 200°C, the substrate with the coating film is placed in the thermostatic bath, and after 10 minutes, the substrate is taken out from the thermostatic bath, and the substrate is placed in a room at room temperature of 25°C to cool the substrate, thereby forming the lower layer of Example 4. Next, a liquid composition B1 is dripped on the surface of the lower layer in an appropriate amount to form a coating film by spin coating. Next, the temperature inside the thermostatic bath is pre-adjusted to 200°C, the substrate with the coating film is placed in the thermostatic bath, and after 10 minutes, the substrate is taken out from the thermostatic bath, and the substrate is placed in a room at room temperature of 25°C to cool the substrate, thereby preparing the anti-reflection film of Example 4.

[0204] <Example 5>

[0205] An antireflection film of Example 5 was produced in the same manner as in Example 4 except that the liquid composition B8 was used instead of the liquid composition B6, and the liquid composition B2 was used instead of the liquid composition B1.

[0206] <Example 6>

[0207] An antireflection film of Example 6 was produced in the same manner as in Example 4, except that liquid composition B7 was used instead of liquid composition B6, and liquid composition B5 was used instead of liquid composition B1.

[0208] <Example 7>

[0209] An antireflection film of Example 7 was produced in the same manner as in Example 4 except that the liquid composition B9 was used instead of the liquid composition B6.

[0210] <Example 8>

[0211] As the substrate, a borosilicate glass material D263 T eco (refractive index n 2.1 mm) manufactured by Corning Incorporated was used. D :1.5230) substrate, the substrate is properly cleaned with an alkaline solution and an organic solvent, and a single-layer film of SiO2 is formed on one main surface of the substrate by vacuum evaporation. The thickness of the SiO2 single-layer film is 103nm. Then, a liquid composition B3 is dripped on the surface of the SiO2 single-layer film in an appropriate amount, and a coating film is formed by spin coating. The temperature inside the thermostatic bath is pre-adjusted to 200°C, and the substrate with the coating film is placed in the thermostatic bath. After 10 minutes, the substrate is taken out of the thermostatic bath, and the substrate is placed in a room at a room temperature of 25°C to cool the substrate, thereby preparing the anti-reflection film of Example 8.

[0212] <Example 9>

[0213] An antireflection film of Example 9 was produced in the same manner as in Example 4 except that the liquid composition B8 was used instead of the liquid composition B6, and the liquid composition B10 was used instead of the liquid composition B1.

[0214] Table 1 shows the antireflection films of the respective Examples and the conditions of the liquid compositions used in producing the antireflection films.

[0215] <Anti-reflection film for fitting>

[0216] In order to fit the reflection spectrum, a film corresponding to the antireflection film of each example was produced on the silicon wafer in the same manner as in each example, except that a silicon wafer was used as a substrate instead of the substrate of D263 T eco.

[0217] <Measurement of reflectance and reflectance spectrum>

[0218] For the anti-reflection film of each example, the reflection spectrum at an incident angle of 5° was measured using a UV-visible near-infrared spectrophotometer V-770 manufactured by JASCO Corporation. Furthermore, the reflectivity at the D line (wavelength 589.6nm) was obtained as a representative reflectivity. The results are shown in Table 2. In addition, the reflection spectrum of the film formed on the silicon wafer was measured in the same manner. The reflection spectra of the anti-reflection films of Example 1, Example 4, Example 5 and Example 7 are shown in Table 2. Figure 5 , Figure 6 , Figure 7 and Figure 8 .

[0219] <Observation of Cross Section of Antireflection Film>

[0220] The anti-reflection film of each example was cut along a surface perpendicular to the main surface of the substrate, and the cut surface was subjected to a conductive treatment by carbon evaporation to prepare a sample. The sample was observed using a field emission scanning electron microscope (FE-SEM) SU8220 manufactured by Hitachi High-Technologies Corporation, and a 100,000-fold SEM image of the cross section of the anti-reflection film of each example was obtained. In the 100,000-fold SEM image of the cross section of the anti-reflection film of each example, a 500 nm square area was determined in a manner that includes all layers in the thickness direction, and the particles existing in the area were determined, and the outline of each particle was approximated by a circle. In the circle that approximated the outline of the particles existing in the 500 nm square area, particles that can identify more than half of the area of ​​the circle were determined and the diameters of these circles were measured, and the measured values ​​were determined as the diameters of each particle diameter. The arithmetic average of the diameters of all particles existing in the 500 nm square area was calculated, and the average particle size D of the particles contained in each layer of the anti-reflection film of each example was calculated. p .

[0221] In addition, in each SEM image of the cross section of the antireflection film of Examples 4 to 9, a 500 nm square area was determined so as to include all layers in the thickness direction, and particles approximated by a circle were determined, and the number N of particles partially buried in the layer close to the substrate at the boundary between the layers was calculated. M1 In addition, the area S of the approximate circle of the particle partially buried in the layer close to the substrate at the boundary between the layers is calculated. L and the area S corresponding to the circular portion of the buried portion of the approximate circle M , find the ratio S M / S L .

[0222] In each of the above SEM images, after determining an approximate straight line corresponding to the surface of the substrate, the boundary line of each layer is determined in parallel with the line, and the thickness of each layer is measured. In the SEM images of the cross section of the antireflection film of Examples 1 to 3, the thickness t of the entire layer including the first layer and the second layer is measured. LL In the SEM images of the cross sections of the antireflection films of Examples 4 and 7, the thickness t of the entire layer including the first layer and the second layer was measured. LL The thickness of the third layer t M3 In the SEM images of the cross sections of the antireflection films of Examples 5 and 6, the thickness t of the entire layer including the first layer and the second layer was measured. LL , and the thickness t of the layer including the third layer and the fourth layer MM In Examples 1 to 3, the first layer and the second layer are sequentially arranged toward the substrate. In Examples 4 and 7, the first layer, the second layer, and the third layer are sequentially arranged toward the substrate. In Examples 5 and 6, the first layer, the second layer, the third layer, and the fourth layer are sequentially arranged toward the substrate. Fig. 9 This is a SEM image of a cross section of the antireflection film of Example 1. Fig.10 This is a SEM image of a cross section of the antireflection film of Example 5. Fig. 9 and Fig.10 The area surrounded by the white dotted line indicates the average particle size D p , the number of particles N M1 , than S M / S L And select the area of ​​500nm square.

[0223] <Fitting of reflectance spectrum>

[0224] TFCalc (registered trademark), an optical thin film coating characteristic calculation software manufactured by HULINKS, was used to fit the measured reflection spectrum of the film of each embodiment formed on the silicon wafer and the reflection spectrum calculated by simulation, thereby calculating the refractive index and thickness of the layer contained in each film of each embodiment. The refractive index and thickness calculated in this way can be regarded as the refractive index and thickness of each layer in the anti-reflection film of each embodiment.

[0225] For Examples 1 to 3, the refractive index n of the first layer was determined. L1 , the refractive index of the second layer n L2 , the thickness of the first layer t L1 and the thickness of the second layer t L2 The thickness of the second layer is t L2 It can be assumed that the binder contained in the second layer is localized on the surface of the second layer and the substrate, and the thickness can be assumed to be t L2 is 2nm.

[0226] For Examples 4 and 7, the refractive index n of the first layer is obtained. L1 , the refractive index of the second layer n L2 , the refractive index of the third layer n L3 , the thickness of the first layer t L1 , the thickness of the second layer t L2 and the thickness of the third layer t M3 The thickness of the second layer is t L2 It can be assumed that the binder contained in the second layer is localized on the surface of the second layer and the substrate, and the thickness can be assumed to be t L2 is 2nm.

[0227] For Examples 5, 6 and 9, the refractive index n of the first layer is obtained. L1 , the refractive index of the second layer n L2 , the refractive index of the third layer n L3 , the refractive index of the fourth layer n L4 , the thickness of the first layer t L1 , the thickness of the second layer t L2 , the thickness of the third layer t M3 and the thickness of the fourth layer t M4 The thickness of the second layer is t L2 The sum of the thickness of the outer shell of the hollow fine particles contained in the third layer, ie, 14 nm, and the thickness of the binder localized at the boundary between the first layer and the second layer, ie, 2 nm, can be assumed to be 16 nm.

[0228] <Adhesion Test>

[0229] The adhesion test of the anti-reflection film of the embodiment was conducted according to the conditions and method (cross-cut peeling test) of Japanese Industrial Standard (JIS) K5600-5-6. Six vertical and horizontal cutting lines were drawn at 1 mm intervals on the surface of the anti-reflection film of the embodiment to form a cutting line pattern that constituted a grid of 25 squares with a side length of 1 mm when viewed from above. The substrate with the anti-reflection film was placed on a flat glass table and the anti-reflection film was subjected to a force of 3.3 N / cm 2 The tape was pressed against the surface of the anti-reflection film, and the end of the tape was lifted at an angle of 60° while being peeled off from the surface of the anti-reflection film in 1 second. The tape used was Cellotape CRCT-18 for clean rooms manufactured by Nichiban Co., Ltd. Cellotape is a registered trademark. The tape was applied and peeled off twice on the entire surface of the anti-reflection film on which a cutting line pattern was formed. The adhesion of each anti-reflection film was evaluated according to the following evaluation criteria. The results are shown in Table 2. As shown in Table 2, the anti-reflection films of Examples 1 to 8 have high adhesion relative to the anti-reflection film of Example 9.

[0230] A: The number of peeled meshes among 25 meshes is 0.

[0231] B: The number of peeled meshes among 25 meshes is 0 or more and less than 5%.

[0232] C: The number of peeled meshes among 25 meshes is 5% or more and less than 15%. D: The number of peeled meshes among 25 meshes is 15% or more and less than 35%. E: The number of peeled meshes among 25 meshes is 35% or more.

[0233]

[0234]

Claims

1. An anti-reflection film, which is an anti-reflection film provided on a substrate, wherein: The antireflection film includes a first layer and a second layer in order from the surface side of the antireflection film, The first layer has a refractive index n of 1.10 to 1.35 L1 and a thickness of 80nm to 150nm, The second layer has a refractive index n of 1.30 to 1.55 L2 and thickness below 25nm.

2. The antireflection film according to claim 1, which satisfies n L1 <n L2 conditions.

3. The antireflection film according to claim 1 or 2, wherein: The antireflection film includes first hollow fine particles and a first binder for binding the first hollow fine particles. The content of the first hollow fine particles in the antireflection film is 80% to 99.5% by mass.

4. The antireflection film according to claim 3, wherein: The first hollow particles have an average particle size D of 5 nm to 200 nm. p .

5. The antireflection film according to claim 3 or 4, wherein: The first binder includes at least one selected from the group consisting of alkoxysilane, a hydrolyzate of alkoxysilane, and a polymer of a hydrolyzate of alkoxysilane.

6. The antireflection film according to any one of claims 1 to 5, wherein The minimum reflectivity in the wavelength range of 400 nm to 800 nm is 0.5% or less.

7. The antireflection film according to any one of claims 1 to 6, wherein The range of reflectivity below 1% in the wavelength range of 300nm to 1200nm range / 1.0 It is above 250nm.

8. The antireflection film according to any one of claims 1 to 7, further comprising a third layer disposed between the second layer and the substrate. The third layer has a refractive index n of 1.30 to 2.

25. L3 and a thickness of 60nm to 200nm.

9. The antireflection film according to claim 8, which satisfies n L1 <n L3 <n L2 conditions.

10. The antireflection film according to claim 8 or 9, wherein: The first layer and the second layer form a first multilayer structure, The first multilayer structure comprises first hollow particles and a first binder for binding the first hollow particles. The third layer contains at least a second binder.

11. The antireflection film according to any one of claims 1 to 7, further comprising: a third layer disposed between the second layer and the substrate; and a fourth layer disposed between the third layer and the substrate, The third layer has a refractive index n of 1.30 to 2.

25. L3 and a thickness of 60nm to 200nm, The fourth layer has a refractive index n of 1.30 to 1.

55. L4 and thickness below 25nm.

12. The antireflection film according to claim 11, wherein The first layer and the second layer form a first multilayer structure, The third layer and the fourth layer form a second multi-layer structure, The first multilayer structure comprises first hollow particles and a first binder for binding the first hollow particles. The second multilayer structure includes second hollow particles and a second binder for binding the second hollow particles.

13. The antireflection film according to claim 12, wherein: The difference between the refractive index of the first adhesive and the refractive index of the second adhesive is 0.01 or less.

14. A liquid composition comprising: first hollow microparticles; and At least one selected from the group consisting of alkoxysilane and hydrolyzate of alkoxysilane, The mass ratio of the first hollow fine particles to the solid content of the liquid composition is 80% to 99.5%.

15. The liquid composition according to claim 14, wherein The alkoxysilane comprises tetrafunctional alkoxysilane and trifunctional alkoxysilane, The ratio of the amount of the tetrafunctional alkoxysilane to the amount of the trifunctional alkoxysilane is 1 / 9 to 9.

16. A liquid composition comprising: a first liquid composition comprising first hollow particles and a precursor of a first binder; and a second liquid composition comprising a precursor of second hollow particles and a second binder, The first liquid composition can form a first layer and a first portion of a second layer by solidifying the first liquid composition. The second liquid composition can form the second portion of the second layer, the third layer, and the fourth layer by solidifying the second liquid composition.

17. The liquid composition set according to claim 16, wherein: The first layer has a refractive index n of 1.10 to 1.35 L1 and a thickness of 80nm to 150nm, The second layer has a refractive index n of 1.30 to 1.55 L2 and thickness below 25nm, The third layer has a refractive index n of 1.30 to 2.

25. L3 and a thickness of 60nm to 200nm, The fourth layer has a refractive index n of 1.30 to 1.

55. L4 and thickness below 25nm.

18. The liquid composition set according to claim 16 or 17, wherein: The mass ratio of the solid content of the first hollow fine particles to the solid content of the first liquid composition is greater than the mass ratio of the solid content of the second hollow fine particles to the solid content of the second liquid composition.

19. A method for manufacturing an anti-reflection film, comprising: applying a first liquid composition on a substrate, the first liquid composition comprising first hollow fine particles and at least one selected from the group consisting of alkoxysilane and a hydrolyzate of alkoxysilane; and solidifying the first liquid composition, The mass ratio of the first hollow particles to the first liquid composition is 80% to 99.5%. The anti-reflection film includes a first layer and a second layer separated in order from a surface of the anti-reflection film.

20. The method for producing an antireflection film according to claim 19, wherein: The first layer has a refractive index n of 1.10 to 1.35 L1 and a thickness of 80nm to 150nm, The second layer has a refractive index n of 1.30 to 1.55 L2 and thickness below 25nm, Satisfy n L1 <n L2 conditions.

21. The method for producing an antireflection film according to claim 19 or 20, wherein: The antireflection film has a minimum reflectivity of 0.5% or less in the wavelength range of 400 nm to 800 nm and a reflectivity of 1% or less in the wavelength range of 300 nm to 1200 nm. range / 1.0 It is the reflection spectrum above 250nm.

22. The method for producing an antireflection film according to any one of claims 19 to 21, wherein: The second layer includes a portion of the outer shell of the first hollow fine particles and a portion of the polymer of the hydrolyzate of the alkoxysilane.

23. A method for manufacturing an anti-reflection film, comprising: forming a third layer comprising a dielectric on the substrate; applying a first liquid composition on the surface of the third layer, wherein the first liquid composition comprises first hollow fine particles and at least one selected from the group consisting of alkoxysilane and a hydrolyzate of alkoxysilane; and solidifying the first liquid composition, The anti-reflection film includes a first layer and a second layer separated in order from the surface of the anti-reflection film, The first layer has a refractive index n of 1.10 to 1.35 L1 and a thickness of 80nm to 150nm, The second layer has a refractive index n of 1.30 to 1.55 L2 and thickness below 25nm, The third layer has a refractive index n of 1.30 to 2.

25. L3 and a thickness of 60nm to 200nm, Satisfy n L1 <n L2 conditions.

24. The method for producing an antireflection film according to claim 23, wherein: The third layer comprises the following layers (i) and / or (ii), (i) a layer comprising a dielectric film, the dielectric film comprising one or two or more oxides selected from the group consisting of SiO2, MgF2, TiO2, Ta2O3, AlF3, CaF2, Al2O3, ZrO2, WO3, CeO2, indium tin oxide and antimony tin oxide; (ii) A layer comprising oxide particles and a binder for bonding the oxide particles, wherein the oxide particles are composed of one or more materials selected from the group consisting of SiO2, TiO2, ZrO2, CeO2, indium tin oxide and antimony tin oxide.

25. A method for manufacturing an anti-reflection film, comprising: applying a second liquid composition on a substrate, the second liquid composition comprising second fine particles containing an oxide and at least one selected from the group consisting of alkoxysilane and a hydrolyzate of alkoxysilane; solidifying the second liquid composition; applying a first liquid composition comprising first hollow fine particles and at least one selected from the group consisting of alkoxysilane and a hydrolyzate of alkoxysilane on a surface of the cured product of the second liquid composition; and solidifying the first liquid composition, The anti-reflection film includes a first layer, a second layer, a third layer, and a fourth layer separated in order from the surface of the anti-reflection film, The second layer includes a portion of the outer shell of the first hollow fine particles, a portion of the polymer of the hydrolyzate of alkoxysilane, and a portion of the second fine particles.

26. The method for producing an antireflection film according to claim 25, wherein: The first layer has a refractive index n of 1.10 to 1.35 L1 and a thickness of 80nm to 150nm, The second layer has a refractive index n of 1.30 to 1.55 L2 and thickness below 25nm, The third layer has a refractive index n of 1.30 to 2.

25. L3 and a thickness of 60nm to 200nm, The fourth layer has a refractive index n of 1.30 to 1.

55. L4 and thickness below 25nm, Satisfy n L1 <n L2 and n L3 <n L4 conditions.

27. The method for producing an antireflection film according to claim 25 or 26, wherein: The mass ratio of the first hollow particles to the first liquid composition is 80% to 99.5%. The mass ratio of the second fine particles to the second liquid composition is 5% to 75%.

Images