JP4400211B2 - Low reflection laminate and method for producing low reflection laminate - Google Patents

Description

  The present invention relates to a low antireflection laminate and a method for producing a low reflection laminate.

  Many image display devices such as flat panel displays (FPD) such as liquid crystal display devices (LCD) and plasma display panels (PDP) and cathode ray tube display devices have an environment in which external light or the like is incident both indoors and outdoors. Since it is used below, there is an increasing demand for prevention of reflection of external light, that is, prevention of reflection for improving visibility. Therefore, an antireflection film has been increasingly provided on the display surface for easier viewing. As the antireflection film, a single layer structure in which a low refractive index layer having a low refractive index is provided on the surface or a multilayer film in which a transparent thin film of metal oxide is laminated has been conventionally used. When a plurality of transparent thin films are used, reflection of light having a wide range of wavelengths can be prevented or reduced. Therefore, the visibility can be further improved by forming the antireflection film in a multilayer structure.

  Conventionally, a transparent thin film of metal oxide used for an antireflection film has been formed by a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method, or a method of applying inorganic fine particles and a binder polymer. However, in general, the multilayer film formed by the vapor deposition method has excellent optical properties, but has the disadvantage that the productivity is extremely low and is not suitable for mass production. On the other hand, the multilayer film formed by the coating method is not suitable. Although the productivity is high, there is a problem that it is inferior to the vapor deposition method in terms of optical characteristics and surface physical properties.

  Further, since the antireflection film is installed on the outer surface of the image display device, high light resistance is required. However, titanium dioxide fine particles suitably used for the medium refractive index layer or the high refractive index layer in the coating method have a photocatalytic function. Therefore, there is a problem that adjacent organic compounds are decomposed and physical properties and transparency are remarkably deteriorated. Furthermore, when an ultraviolet curable resin is applied as a binder, ultraviolet curing proceeds by light irradiation, causing binder shrinkage, film shrinkage, refractive index change, and significant deterioration of film physical properties. . To solve this problem, a method of applying inorganic fine particles having a core / shell structure has been disclosed (see, for example, Patent Document 1), but this method tends to suppress the photocatalytic action of titanium dioxide fine particles. The shrinkage of the UV curable resin could not be suppressed.

  On the other hand, in order to reduce the reflectance of the low-reflection laminate, the refractive index of the outermost low-refractive index layer may be lowered. For this purpose, the refractive index can be lowered to some extent by using silicon dioxide or magnesium fluoride. However, it does not drop below the intrinsic refractive index of the material used. Therefore, since the refractive index of air is approximately 1, it is considered that the refractive index can be further reduced by using a material containing air in the substance. For example, hollow fine particles or fine particles having a porous structure Studies have been made to further reduce the refractive index by using (see, for example, Patent Documents 2 to 4). However, since such fine particles have weak binding between the fine particles or become bulky fine particles, it is difficult to obtain sufficient film strength as the outermost low refractive index layer, and the scratch resistance is deteriorated.

  On the other hand, the low refractive index layer using a sol-gel material such as metal alcoholate has a slightly higher refractive index than the low refractive index layer containing hollow fine particles and fine particles having a porous structure, but has a slightly higher refractive index. Thus, a strong matrix can be formed, so that a layer having high film strength and excellent scratch resistance can be formed.

  However, the layer formed by the sol-gel method has a limit in reducing the refractive index as described above, and it is difficult to completely complete the sol-gel reaction, and the film may shrink over time. In this case, the low reflective layer may be cracked depending on the combination of the layer configuration of the low reflective laminate, the rate of shrinkage, and the shrinkage rate. In particular, a layer formed on a plastic film has a limit in reaction completion by heating, and cracks easily occur over time.

From the above, there is a demand for further improvements in antireflection properties and film strength.
JP 2001-166104 A Japanese Patent Laid-Open No. 2001-167637 JP 2001-233611 A JP 2002-79616 A

  An object of the present invention is to provide a low-reflection layered product and a method for producing the low-reflection layered product. Specifically, the low-reflection layered product has a sufficiently low reflectance, and scratch resistance, crack resistance, and adhesion are improved. Another object of the present invention is to provide a low reflection preventive laminate and a method for producing the low reflection laminate.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A composite particle having at least two low-refractive index layers on a base material, wherein at least the base-side layer of the low-refractive index layer has fine particles as a porous particle and a coating layer provided on the surface of the porous particle; Alternatively, it contains hollow particles filled with a solvent, gas, or porous substance inside, the fine particle content and film thickness of the layer on the base material side are A and a, respectively, and the surface side layer is a solution of an alkoxysilicon compound. A silicon dioxide matrix using a hydrolyzate obtained by decomposition and condensation of an alkoxysilicon compound, wherein the following formulas I and II are satisfied when the fine particle content and film thickness of the surface-side layer are B and b, respectively: A low-reflection laminate characterized by the above.
Formula IA>B> 0
Formula II a ≧ b

(Claim 2)
2. The low reflection laminate according to claim 1, wherein the total thickness of the low refractive index layers is 50 to 200 nm.

(Claim 3)
The low reflective laminated body of Claim 1 or 2 which has at least 1 layer chosen from a medium refractive index layer and a high refractive index layer in the base material side rather than a low refractive index layer.

(Claim 4)
In producing a low reflective laminate having at least two low refractive index layers on a substrate, composite particles having porous particles and a coating layer provided on the surface of the porous particles, or a solvent, gas inside, Alternatively, after applying a low refractive index layer containing hollow particles filled with a porous material, a low refractive index layer containing an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing an alkoxysilicon compound is applied to a sol-gel reaction. A method for producing a low-reflection laminate, comprising: laminating by:

(Claim 5)
On the low-refractive index layer containing composite particles having porous particles and a coating layer provided on the surface of the porous particles, or hollow particles filled with a solvent, gas, or porous substance inside, the alkoxysilicon The method for producing a low reflection laminate according to claim 4, wherein a low refractive index layer containing an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing a compound is laminated on a wet on wet basis.

  According to the present invention, it is possible to provide a low antireflection laminate having a sufficiently low reflectance and improved scratch resistance, crack resistance and adhesion, and a method for producing the low reflection laminate.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

It is an object of the present invention to have at least two low-refractive index layers on a base material, and at least the base-side layer of the low-refractive index layer is provided as porous particles and a coating provided on the surface of the porous particles Composite particles having layers, or hollow particles filled with a solvent, gas, or porous substance inside, and the fine particle content and film thickness of the substrate side layer are A and a, respectively, and the surface side layer Is a silicon dioxide matrix using an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing an alkoxysilicon compound, and when the fine particle content and film thickness of the surface-side layer are B and b, respectively, This is achieved by a low reflection laminate characterized by satisfying I and II .
Formula IA>B> 0
Formula II a ≧ b

  That is, if the low refractive index layer on the substrate is composed of at least two layers and a matrix layer (hereinafter also referred to as sol-gel layer) by a sol-gel reaction is provided on the layer containing a large amount of fine particles, a strong sol-gel film is the outermost surface. Therefore, a low refractive index layer excellent in scratch resistance can be formed. In addition, the optically necessary film thickness and refractive index of the low-reflection laminate can be ensured by the fine particle-containing layer, and the reflectance of the low-reflection laminate can be lowered by adjusting the film thickness of the fine particle layer and the sol-gel layer. I can do it. In particular, if the surface sol-gel layer is thinned within a range where the film strength can be obtained, the effect of reducing the reflectance is high. Further, by providing the sol-gel layer on the fine particle layer, the stress due to the shrinkage of the sol-gel layer is relieved by the fine particle layer, so that cracks are hardly generated. Since the stress generated in the sol-gel layer can be reduced by reducing the thickness of the sol-gel layer as described above, the crack prevention effect can be enhanced. Furthermore, the binder of the fine particle layer is a silicon dioxide matrix produced by the sol-gel method, and the same or similar configuration as that of the sol-gel layer laminated on it, so that these two layers are integrated, and the film strength of the adhesiveness and low refractive index layer Can be improved dramatically.

  In this case, the above effect can be further enhanced by laminating the sol-gel layer before proceeding with the sol-gel reaction of the binder of the fine particle layer and then proceeding with the reaction.

  Alternatively, when the fine particle layer is provided, the binder component is not added or reduced, and the sol-gel layer is laminated thereon, so that the sol-gel binder is infiltrated between the fine particles to form the low refractive index layer. The film strength can be increased at the same time while increasing the content to reduce the refractive index and reflectivity. In this case, it is preferable that the amount of fine particles is large in the layer on the substrate side and small in the surface side layer, and the surface side layer is substantially a sol-gel layer.

  At that time, by applying the sol-gel layer wet-on-wet, the penetration of the sol-gel layer into the fine particle layer becomes more effective, and it becomes easy to achieve both reflectivity and film strength. Depending on the type of low-refractive index material, coating on the fine particle layer tends to cause unevenness due to the relatively disturbed film surface, so if we apply wet-on-wet, this problem of applicability can be solved. I can do it.

  Hereinafter, the present invention will be described in detail.

(Low reflective layer)
In the low reflection laminate according to the present invention, the metal oxide layer may be directly formed on the transparent base film described below, but at least one other coating layer is provided, and the long base film having an uneven surface It may be formed on the top. The other coating layer is preferably an actinic radiation curable resin layer described later having a centerline average surface roughness (Ra) defined by JIS B 0601 of 0.01 to 1 μm. These are resin layers that are cured by active rays such as ultraviolet rays. By coating a metal oxide layer on the resin layer cured with such ultraviolet rays, an excellent low reflection laminate with reduced generation of transport scratches and cracks can be obtained.

  The basic configuration of the low reflection laminate of the present invention will be described. For example, the low reflective laminate is a transparent support / hard coat layer / low refractive index layer, transparent support / hard coat layer / high refractive index layer / low refractive index layer, transparent support / hard coat layer / medium refractive index. Layer / high refractive index layer / low refractive index layer in order, transparent support / hard coat layer / high refractive index layer / low refractive index layer, transparent support / hard coat layer / medium refractive index layer / High refractive index layer / Low refractive index layer is preferable. In any case, the low refractive index layer has at least two layers, and the content of fine particles needs to satisfy the formula I.

  The transparent support, the middle refractive index layer, the high refractive index layer, and the low refractive index layer have a refractive index that satisfies the following relationship.

  The refractive index of the low refractive index layer <the refractive index of the transparent support <the refractive index of the medium refractive index layer <the refractive index of the high refractive index layer.

  In a low reflection laminate having a medium refractive index layer, a high refractive index layer, and a low refractive index layer, as described in JP-A-59-50401, the medium refractive index layer has the following formula (1): When the refractive index layer satisfies the following mathematical formula (2) and the low refractive index layer satisfies the following mathematical formula (3), it is possible to further reduce the average reflectance of the low reflective laminate, which is preferable.

(Hλ / 4) × 0.7 <n ₃ d ₃ <(hλ / 4) × 1.3 (1)
In formula (1), h is a positive integer (generally 1, 2 or 3), n ₃ is the refractive index of the medium refractive index layer, and d ₃ is the film thickness (nm) of the medium refractive index layer. It is. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

(Jλ / 4) × 0.7 <n ₄ d ₄ <(jλ / 4) × 1.3 (2)
In formula (2), j is a positive integer (generally 1, 2 or 3), n ₄ is the refractive index of the high refractive index layer, and d ₄ is the film thickness (nm) of the high refractive index layer. It is. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

(Kλ / 4) × 0.7 <n ₅ d ₅ <(kλ / 4) × 1.3 (3)
In Equation (3), k is a positive odd number (generally 1), n ₅ is the refractive index of the low refractive index layer, and d ₅ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 350 to 800 (nm).

  Moreover, in this invention, it is also preferable to give an unevenness | corrugation to a hard-coat layer or a high refractive index layer, and to set it as an anti-glare low reflection laminated body.

  In addition, a layer structure in the order of a transparent support, a hard coat layer (antiglare layer), a high refractive index layer, a low refractive index layer, a high refractive index layer, and a low refractive index layer is also a preferable configuration. An antiglare property can be imparted to the low refractive index layer on the surface, and an antiglare layer may be provided on the surface.

(Low refractive index layer)
The low refractive index layer according to the present invention has at least two low refractive index layers on a substrate, and at least the substrate side layer of the low refractive index layer is a porous particle and the porous particle surface Composite particles having a coating layer provided on the inside, or hollow particles filled with a solvent, gas, or porous substance inside, and the fine particle content and film thickness of the layer on the substrate side are respectively A and a The surface-side layer is a silicon dioxide matrix using an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing an alkoxysilicon compound, and the fine particle content and film thickness of the surface-side layer are B and b, respectively. This is achieved by a low reflection laminate characterized by satisfying the following formulas I and II .

Formula IA>B> 0
Formula II a ≧ b
That is, as a low refractive index layer, it is necessary that the layers of the substrate side contains mainly inorganic or organic fine particles, fine particles content of the surface side layer has less than the layer of the substrate side.

  The fine particles used in the low refractive index layer are preferably the following particles, and it is also preferred to use a layer formed as a micro void between or within the fine particles. The average particle diameter of the fine particles is preferably 0.5 to 200 nm, more preferably 1 to 100 nm, still more preferably 3 to 70 nm, and most preferably in the range of 5 to 40 nm. The particle diameter of the fine particles is preferably as uniform (monodispersed) as possible.

The inorganic fine particles are preferably amorphous. The inorganic fine particles are preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or a metal halide, and most preferably a metal oxide or a metal fluoride. . As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb and Ni are preferable, and Mg, Ca, B and Si are more preferable. An inorganic compound containing two kinds of metals may be used. Specific examples of preferred inorganic compounds are SiO ₂ and MgF ₂ , and particularly preferred is SiO ₂ .

Particles having microvoids in the inorganic fine particles can be formed, for example, by crosslinking silica molecules forming the particles. Crosslinking silica molecules reduces the volume and makes the particles porous. (Porous) inorganic fine particles having microvoids are prepared by a sol-gel method (described in JP-A-53-112732 and JP-B-57-9051) or a precipitation method (described in APPLIED OPTICS, 27, 3356 (1988)). Can be directly synthesized as a dispersion. Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, SiO ₂ sol) may be used.

  These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone) are preferable.

  The organic fine particles are also preferably amorphous. The organic fine particles are preferably polymer fine particles synthesized by polymerization reaction of monomers (for example, emulsion polymerization method). The organic fine particle polymer preferably contains a fluorine atom. The proportion of fluorine atoms in the polymer is preferably 35 to 80% by mass, and more preferably 45 to 75% by mass. It is also preferable to form microvoids in the organic fine particles by, for example, cross-linking the polymer forming the particles and reducing the volume. In order to crosslink the polymer forming the particles, it is preferable to use 20 mol% or more of the monomer for synthesizing the polymer as a polyfunctional monomer. The ratio of the polyfunctional monomer is more preferably 30 to 80 mol%, and most preferably 35 to 50 mol%. Examples of the monomer used for the synthesis of the organic fine particles include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene) as examples of monomers containing fluorine atoms used to synthesize fluorine-containing polymers. , Perfluoro-2,2-dimethyl-1,3-dioxole), fluorinated alkyl esters of acrylic acid or methacrylic acid, and fluorinated vinyl ethers. A copolymer of a monomer containing a fluorine atom and a monomer not containing a fluorine atom may be used. Examples of monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic esters (eg, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate). , Methacrylates (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate), styrenes (eg, styrene, vinyl toluene, α-methyl styrene), vinyl ethers (eg, methyl vinyl ether), vinyl esters ( Examples thereof include vinyl acetate and vinyl propionate), acrylamides (for example, N-tert-butylacrylamide, N-cyclohexylacrylamide), methacrylamides and acrylonitriles. Examples of polyfunctional monomers include dienes (eg, butadiene, pentadiene), esters of polyhydric alcohols and acrylic acid (eg, ethylene glycol diacrylate, 1,4-cyclohexane diacrylate, dipentaerythritol hexaacrylate), Esters of polyhydric alcohol and methacrylic acid (for example, ethylene glycol dimethacrylate, 1,2,4-cyclohexanetetramethacrylate, pentaerythritol tetramethacrylate), divinyl compounds (for example, divinylcyclohexane, 1,4-divinylbenzene), divinyl Examples include sulfones, bisacrylamides (eg, methylenebisacrylamide) and bismethacrylamides.

  Microvoids between particles can be formed by stacking at least two fine particles. When spherical particles having the same particle diameter (completely monodispersed) are closely packed, microvoids between particles with a porosity of 26% by volume are formed. When spherical fine particles having the same particle diameter are simply filled with cubic particles, microvoids between fine particles having a porosity of 48% by volume are formed. In an actual low-refractive index layer, the particle size distribution of fine particles and intra-particle microvoids exist, so the porosity varies considerably from the above theoretical value. When the porosity is increased, the refractive index of the low refractive index layer is lowered. When microvoids are formed by stacking fine particles, the size of the microvoids can be adjusted to an appropriate value (does not scatter light and cause no problem with the strength of the low refractive index layer) by adjusting the particle size of the fine particles. You can adjust. Furthermore, by making the particle diameters of the fine particles uniform, it is possible to obtain an optically uniform low refractive index layer in which the size of microvoids between particles is uniform. As a result, the low refractive index layer is microscopically a microvoided porous film, but can be made optically or macroscopically uniform. The interparticle microvoids are preferably closed in the low refractive index layer by fine particles and a polymer. The closed air gap also has an advantage that light scattering on the surface of the low refractive index layer is less than that of an opening opened on the surface of the low refractive index layer.

  By forming the microvoids, the macroscopic refractive index of the low refractive index layer becomes lower than the sum of the refractive indexes of the components constituting the low refractive index layer. The refractive index of the layer is the sum of the refractive indices per volume of the layer components. The refractive index of the constituent component of the low refractive index layer such as fine particles or polymer is larger than 1, whereas the refractive index of air is 1.00. Therefore, a low refractive index layer having a very low refractive index can be obtained by forming microvoids.

Is containing organic in the low refractive index layer of the present invention, porous particles and said porous composite particles having a coating layer formed on the particle surface, or internal solvent, gas or hollow particles filled with a porous material, Will be described.

  The inorganic fine particle is (I) a composite particle comprising a porous particle and a coating layer provided on the surface of the porous particle, or (II) a cavity inside, and the content is a solvent, a gas or a porous substance It is a hollow particle filled with. The low refractive index layer may contain either (I) composite particles or (II) hollow particles, or may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with a content such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle diameter of such inorganic fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The average particle diameter of the inorganic fine particles used is appropriately selected according to the thickness of the transparent film to be formed, and is in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. It is desirable to be in These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and silicate monomers and oligomers with a low degree of polymerization, which are coating liquid components described later, are easy. In some cases, the inside of the composite particle enters the inside and the porosity of the inside is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles preferably contains silica as a main component. Also the particle wall of the covering layer or a hollow particle of the composite particle may contain components other than silica, _{specifically, Al 2 O 3, B 2} O 3, TiO 2, ZrO 2, SnO 2 and _{CeO 2, P 2 O 3,} Sb 2 O 3, MoO 3, ZnO 2, WO 3 and the like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MOX / SiO ₂ when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 to 0.3. It is difficult to obtain porous particles having a molar ratio MOX / SiO ₂ of less than 0.0001, and even if obtained, those having a lower refractive index are not obtained. On the other hand, if the molar ratio MOX / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that particles having a small pore volume and a low refractive index may not be obtained.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  Incidentally, the pore volume of such porous particles can be obtained by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous material used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used in preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such inorganic fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, the inorganic compound particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium Salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. I can do it. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or higher, and then the aqueous solution of the compound is added to the above-mentioned alkaline aqueous solution with stirring. Also in this case, it is not always necessary to control the pH of the dispersion. In this way, when seed particles are used, it is easy to control the particle size of the porous particles to be prepared, and particles having a uniform particle size can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. Particle deposition occurs on the top. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOx), and the molar ratio of MOx / SiO ₂ is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, the molar ratio of MOx / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded via oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, a silicic acid solution obtained by removing the alkali metal salt of silica from the porous particle precursor dispersion obtained in the first step. Alternatively, it is preferable to form a silica protective film by adding a hydrolyzable organosilicon compound. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than the silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. I can do it. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

  The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organosilicon compound used for forming the silica protective film includes a general formula RnSi (OR ′) 4-n [R, R ′: hydrocarbon such as alkyl group, aryl group, vinyl group, acrylic group, etc. An alkoxysilane represented by the group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third step: Formation of silica coating layer In the third step, a hydrolyzable organosilicon compound or silicic acid solution is added to the porous particle dispersion prepared in the second step (in the case of hollow particles, a hollow particle precursor dispersion). Is added to coat the surface of the particles with a hydrolyzable organosilicon compound or a polymer such as a silicic acid solution to form a silica coating layer.

  Examples of the hydrolyzable organosilicon compound used for forming the silica coating layer include the general formula RnSi (OR ′) 4-n [R, R ′: alkyl group, aryl group, vinyl group, acrylic group as described above. Etc., and alkoxysilanes represented by n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. A silicic acid solution may be used in combination with the alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.44. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. The refractive index of the low refractive index layer according to the present invention is preferably 1.30 to 1.50, more preferably 1.35 to 1.49.

In the present invention, commercially available SiO ₂ fine particles can be used. Specific examples of commercially available particles include P-4 manufactured by Catalytic Chemical Industry Co., Ltd.

As the material for the low refractive index layer according to the present invention, it is preferable to use various sol-gel materials.
In particular, the surface-side layer preferably contains a sol-gel material and is formed into a film by the sol-gel method, and the substrate-side layer also preferably contains the same sol-gel material and is preferably formed into a film by the sol-gel method. It is an aspect.

  As such a sol-gel material, metal alcoholates (alcohols such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. Tetraalkoxysilane and its hydrolyzate are particularly preferable.

  In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  The low refractive index layer can also contain a polymer in an amount of 5-50% by weight. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer and performing a polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out a combination of two or all of the above (1) to (3), and to carry out a combination of (1) and (3) or (1) to (3) all of the combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. Surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Particles when made of SiO _2, surface treatment with a silane coupling agent can be particularly effectively conducted. As a specific example of the silane coupling agent, a silane coupling agent described later is preferably used.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Mention may be made of esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

  Further, the low refractive index layer according to the present invention may be a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”).

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemicals) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). The latter can introduce a cross-linked structure by adding a compound having a group that reacts with a functional group in the polymer and one or more reactive groups after copolymerization. No. 147739. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is cross-linked by heating by a cross-linking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the thermosetting type In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, etc., it is an ionizing radiation curable type. .

  Further, in addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each monomer used to form the fluorinated copolymer before cross-linking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, and more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (R) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR) and the like. It is done.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  In order for the low refractive index layer according to the present invention to have antifouling properties, it is also preferred that the surface side layer contains a compound having antifouling properties.

  In order to develop antifouling properties, it is particularly effective to have an alkyl group on the outermost surface of the film, and this object can be achieved by using a material having an alkyl group as a raw material. The alkyl group may be either a fluoroalkyl group or an alkyl group composed only of carbon and hydrogen, but an alkyl group composed only of carbon and hydrogen is preferred from the environmental suitability after decomposition. In addition, regarding the alkyl group, it is important that the cost is low and the hardness of the film can be maintained. In this sense, it is preferably an ethyl group or a methyl group, and more preferably a methyl group. Moreover, as long as said functional group is provided, the compound may contain two or more silicon atoms.

  More preferably, an organosilicon compound having both a hydrolyzable group and an alkyl group is used. The hydrolyzable group in the present invention refers to a functional group that can be polymerized by adding water and hydrogen, and is not particularly limited in the present invention, but preferably includes an alkoxy group and an acetyl group. It is done. An alkoxy group is preferable, and an ethoxy group is more preferable in terms of reactivity and physical properties of the raw material. However, only by polymerization with such a hydrolyzable group, silicon oxide is formed, and such a film does not exhibit antifouling properties.

  Specific examples of the organosilicon compound include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane. , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltri Ethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Pyrtriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, Chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β- Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane , Β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane , Γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxy Silane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glyoxydoxybutyltrimethoxysilane, δ-glyoxydoxybutyltriethoxy Silane, (3,4-epoxy Cyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, γ- (3 , 4-epoxycyclohexyl) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) )Professional Trialkoxysilanes such as rutriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, triacyloxysilanes, triphenoxysilanes; dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldi Ethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxy Silane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methyl Vinyldimethoxysilene, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β- Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxy Cypropylmethyldibutoxyethoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane Γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyl Dialkoxysilanes such as diethoxysilane, diphenoxysilane, diacyloxysilane, trimethylethoxysilane, trimethylmethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, dimethoxymethyl -3,3,3-trifluoropropylsilane, fluoroalkylsilane, hexamethyldisilane, hexamethyldisiloxanes, etc., but are not limited to these, and even if used alone, they are different. More than one species can be used at the same time. In addition, organosilicon compounds other than the above compounds can be used in combination.

  Among the above compounds, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, trimethylethoxysilane, etc. are preferred, and further against silicon A compound having two alkyl groups is preferable, and dimethyldiethoxysilane, dimethyldimethoxysilane and the like are particularly preferable examples.

  Moreover, it is preferable to add a slipping agent to the low refractive index layer or other refractive index layers of the present invention, and scratch resistance can be improved by imparting slipperiness. As the slip agent, silicon oil or a wax-like substance is preferably used. For example, a compound represented by the following general formula is preferable.

General formula R ₁ COR ₂
In the formula, R ₁ represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms. An alkyl group or an alkenyl group is preferable, and an alkyl group or alkenyl group having 16 or more carbon atoms is more preferable. R ₂ represents —OM ₁ group (M ₁ represents an alkali metal such as Na or K), —OH group, —NH ₂ group, or —OR ₃ group (R ₃ represents a saturated or unsaturated group having 12 or more carbon atoms. R ₂ represents a saturated aliphatic hydrocarbon group, preferably an alkyl group or an alkenyl group, and R ₂ is preferably an —OH group, —NH ₂ group, or —OR ₃ group. Specifically, higher fatty acids such as behenic acid, stearamide, and pentacoic acid, or derivatives thereof, and carnauba wax, beeswax, and montan wax containing many of these components as natural products can also be preferably used. Polyorganosiloxane as disclosed in JP-B-53-292, higher fatty acid amide as disclosed in US Pat. No. 4,275,146, JP-B 58-33541, British patent No. 927,446 or JP-A-55-126238 and 58-90633, higher fatty acid esters (fatty acids having 10 to 24 carbon atoms and 10 to 24 carbon atoms). Esters of alcohols), and higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, dicarboxylic acids having up to 10 carbon atoms as disclosed in JP-A-51-37217 A polyester compound comprising an acid and an aliphatic or cycloaliphatic diol, a dicarboxylic acid disclosed in JP-A-7-13292, It can be mentioned oligo polyester or the like from the Le.

For example, the amount of slip agent to be used in the low refractive index layer is preferably ^{0.01mg / m 2 ~10mg / m 2} .

  Each layer of the low refractive index layer according to the present invention is a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). It can be formed by coating. Two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, It is described in Asakura Shoten (1973).

  The total film thickness of the low refractive index layers according to the present invention is preferably 50 to 200 nm, and more preferably 60 to 150 nm.

Further, when the thickness of the at least two layers of the substrate side of the low refractive index layer a layer according to the present invention is a, the thickness of the surface side of the layer is b, is characterized to satisfy the following formula II .

Formula II a ≧ b
More preferably, a> b, and the film thickness can be appropriately adjusted so as to satisfy the film strength and refractive index as described above.

  In the present invention, a low refractive index layer containing an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing an alkoxysilicon compound is formed on the low refractive index layer containing the composite particles or hollow particles by the above coating method. A low refractive index layer containing an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing an alkoxysilicon compound on the low refractive index layer containing the composite particles or the hollow particles is laminated on wet. It is preferable to laminate.

  Further, after laminating at least two low refractive index layers containing an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing an alkoxysilicon compound on a substrate, the sol-gel reaction of the at least two low refractive index layers is performed. It is preferable to proceed simultaneously. In any case, the scratch resistance, crack resistance and adhesion are dramatically improved as described above.

  In the method for producing a low reflective laminate of the present invention, when the prepared coating solution is applied to a support and then dried, it is preferably dried at 60 ° C. or higher, and further dried at 80 ° C. or higher. preferable. Further, drying at a dew point of 20 ° C. or lower is preferable, and drying at 15 ° C. or lower is more preferable. Furthermore, drying is preferably started within 10 seconds after coating on the support, and combining with the above conditions is a preferable production method for obtaining the effects of the present invention.

(High refractive index layer and medium refractive index)
In the present invention, in order to reduce the reflectance, it is preferable to provide a high refractive index layer between the transparent support or the transparent support provided with the hard coat layer and the low refractive index layer. In addition, it is more preferable to provide a middle refractive index layer between the transparent support and the high refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  In the present invention, the high refractive index layer is formed by applying and drying a coating liquid containing a monomer, oligomer or hydrolyzate of an organic titanium compound represented by the following general formula (1). A layer of 1.55 to 2.5 is preferred.

General formula (1)
Ti (OR ¹ ) ₄
In the formula, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O-i- _{C 3 H 7) 4, Ti} (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7) 4 2-10 mer, Ti (O-i-C 3 H 7) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These may be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  In the present invention, it is preferable that the organic titanium compound is added to a solution in which water and an organic solvent described later are sequentially added to the coating solution for the high refractive index layer. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds. If the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and white turbidity. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  The organic solvent according to the present invention is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention preferably occupies 50.0% by mass to 98.0% by mass in the solid content contained in the coating solution. The solid content ratio is more preferably 50% by mass to 90% by mass, and further preferably 55% by mass to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and the medium refractive index layer according to the present invention contain metal oxide particles as fine particles, and further contain a binder polymer.

  When the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness and uniform film of the particles It is possible to obtain a strong coating film having both flexibility.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The weight average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The weight average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are easy to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In the present invention, the treatment may be performed by combining two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in combination in the high refractive index layer and the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  In the high refractive index layer and the medium refractive index layer according to the present invention, it is preferable to use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide, and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Further, it is further preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, the anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated. The linking group that binds the anionic group and the polymer chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the ratio of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably carbon number. 1 to 6 alkyl groups. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by blending a monomer for generating a cross-linked polymer to prepare a coating solution for forming a high refractive index layer and a medium refractive index layer, and is generated by a polymerization reaction simultaneously with or after coating of the coating solution. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method of forming a crosslinked polymer by a polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku Co., Ltd.) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of a hard-coat layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

  In addition to the above-mentioned components (metal oxide particles, polymer, dispersion medium, polymerization initiator, polymerization accelerator), each layer of the low-reflective laminate or coating solution thereof includes a polymerization inhibitor, a leveling agent, a thickener, and coloring. An inhibitor, an ultraviolet absorber, a silane coupling agent, an antistatic agent or an adhesion promoter may be added.

(Transparent substrate film)
Next, the transparent substrate film that can be used in the present invention will be described.

  The transparent substrate film used in the present invention is easy to manufacture, has good adhesion to the actinic radiation curable resin layer, is optically isotropic, and is optically transparent. Etc. are mentioned as preferable requirements.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, a cellulose-ester type film, a polyester-type film, a polycarbonate-type film, a polyarylate-type film, a polysulfone (a polyether sulfone is also included) film, a polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, Polycarbonate film, cycloolefin polymer film (Arton (manufactured by JSR), Onex, Zeonea (above, manufactured by Nippon Zeon Co., Ltd.), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film or glass plate Can be mentioned. Among them, cellulose triacetate film, polycarbonate film, and polysulfone (including polyethersulfone) are preferable, and in the present invention, cellulose ester film (for example, Konicattak product names KC8UX2MW, KC4UX2MW, KC8UY, KC4UY, KC5UN, KC12UR (Konica ( From the viewpoint of production, cost, transparency, isotropy, adhesiveness and the like. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

The optical properties of the substrate film thickness direction retardation R _t is 0Nm～300nm, retardation R ₀ in the plane direction those 0nm~1000nm is preferably used.

  In the present invention, it is preferable to use a cellulose ester film as the substrate film. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, X and Y are active ray curable resin layers on a base film having a mixed fatty acid ester of cellulose in the following range And a low reflection laminate provided with an antireflection layer is preferably used.

2.3 ≦ X + Y ≦ 3.0
0.1 ≦ Y ≦ 1.2
In particular, 2.5 ≦ X + Y ≦ 2.85
It is preferable that 0.3 ≦ Y ≦ 1.2.

  When cellulose ester is used as the substrate film according to the present invention, the cellulose used as the raw material for the cellulose ester is not particularly limited, and examples thereof include cotton linters, wood pulp (derived from conifers and hardwoods), kenaf and the like. . Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid or an organic solvent such as methylene chloride, and It can be obtained by reacting with a cellulose raw material using a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is carried out using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. In addition, the cellulose ester used in the present invention is obtained by mixing and reacting the amount of the acylating agent in accordance with the degree of substitution. In the cellulose ester, these acylating agents react with hydroxyl groups of cellulose molecules. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  The cellulose ester used in the present invention is a mixed fatty acid ester of cellulose in which a propionate group or a butyrate group is bonded in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, or cellulose acetate propionate butyrate. Is particularly preferably used. The butyryl group forming butyrate may be linear or branched.

  Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for a liquid crystal image display device.

  The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably 70,000 to 250,000 because the mechanical strength when molded is strong and an appropriate dope viscosity is preferable, and more preferably 80,000 to 150,000.

  These cellulose esters are pressurized by applying a cellulose ester solution (dope) generally called a solution casting film forming method onto, for example, an endless metal belt for infinite transport or a support for casting of a rotating metal drum. It is preferable to manufacture the dope from a die by casting (casting).

  The organic solvent used for the preparation of these dopes is preferably capable of dissolving the cellulose ester and having an appropriate boiling point, for example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2 -Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3 , 3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, etc. It is possible, organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone, methyl acetoacetate, and the like are preferable organic solvents (i.e., good solvent), and as.

  Moreover, as shown in the following film forming process, it is used from the viewpoint of preventing foaming in the web when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation process. The boiling point of the organic solvent is preferably 30 to 80 ° C. For example, the good solvent described above has a boiling point of methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56.32 ° C), acetone (boiling point 56.56 ° C). 3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.

  Among the good solvents described above, methylene chloride or methyl acetate, which is excellent in solubility, is preferably used.

  It is preferable to contain 0.1 mass%-40 mass% of C1-C4 alcohol other than the said organic solvent. It is particularly preferable that the alcohol is contained at 5 to 30% by mass. After casting the dope described above onto a casting support, the solvent starts to evaporate and the alcohol ratio increases and the web (dope film) gels, making the web strong and peeling from the casting support. It is also used as a gelling solvent for facilitating, and when these ratios are small, it also has a role of promoting the dissolution of the cellulose ester of a non-chlorine organic solvent.

  Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like.

  Of these solvents, ethanol is preferred because it has good dope stability, relatively low boiling point, good drying properties, and no toxicity. It is preferable to use a solvent containing 5% by mass to 30% by mass of ethanol with respect to 70% by mass to 95% by mass of methylene chloride. Methyl acetate can be used in place of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.

  The cellulose ester film used in the present invention is preferably at least stretched in the width direction, and is 1.01 times to the width direction when the residual solvent amount is 3% by mass to 40% by mass in the solution casting process. The film is preferably stretched 1.5 times. More preferably, biaxial stretching is performed in the width direction and the longitudinal direction, and when the residual solvent is 3% by mass to 40% by mass, the width direction and the longitudinal direction are 1.01 times to 1.5 times, respectively. It is desirable to be stretched. By doing in this way, the light diffusable film excellent in planarity and light diffusibility can be obtained.

  The residual solvent amount is represented by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of the web (cellulose ester film containing the solvent) at an arbitrary point in time, and N is the mass when the web of M is dried at 110 ° C. for 3 hours.

  Furthermore, by carrying out biaxial stretching and performing the knurling described above, it is possible to remarkably improve the deterioration of the winding shape during storage of the long optical film in the form of a roll.

  In the present invention, the biaxially stretched cellulose ester film is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

The cellulose ester film support according to the present invention preferably has a thickness of 10 μm to 100 μm, more preferably 40 μm to 80 μm, and moisture permeability conforms to JIS Z 0208 (25 ° C., 90% RH). The measured value is preferably 200 g / m ² · 24 hours or less, more preferably 10 to 180 g / m ² · 24 hours or less, and particularly preferably 160 g / m ² · 24 hours or less. . In particular, it is preferable that the film thickness is 10 μm to 80 μm and the moisture permeability is within the above range.

  In the present invention, it is preferable to use a long film, and specifically, a film having a length of about 100 m to 5000 m is shown, usually in the form of a roll. Moreover, it is preferable that the width | variety of a base film is 1.3-4 m.

  When a cellulose ester film is used for the low reflection laminate of the present invention, it is preferable to contain the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer or the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, and other trimellitic acid plasticizers include tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include trimethylolpropane tribenzoate, butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid and a glycol can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid and the like can be used. As the glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The amount of these plasticizers used is preferably 1% by mass to 20% by mass and particularly preferably 3% by mass to 13% by mass with respect to the cellulose ester in terms of film performance, processability and the like.

  For the long film for the low reflection laminate of the present invention, an ultraviolet absorber is preferably used.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having a small absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of the ultraviolet absorber preferably used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these.

  Specific examples of the benzotriazole-based ultraviolet absorbers include the following ultraviolet absorbers, but the present invention is not limited thereto.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
Moreover, although the following specific example is shown as a benzophenone series ultraviolet absorber, this invention is not limited to these.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and unnecessary coloring is less. A benzotriazole-based ultraviolet absorber is particularly preferably used.

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorbers described in the general formula (1) or general formula (2) described in JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039 ( Alternatively, an ultraviolet absorbing polymer) is also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

  Moreover, in order to provide slipperiness to the cellulose-ester film used for this invention, the microparticles | fine-particles similar to what is described with the coating layer containing the below-mentioned actinic radiation curable resin can be used.

  The primary average particle diameter of the fine particles added to the cellulose ester film used in the present invention is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm. These fine particles preferably form secondary particles having a particle diameter of 0.1 to 5 μm and are contained in the cellulose ester film, and the preferable average particle diameter is 0.1 to 2 μm, more preferably 0.2 to 0.6 μm. Thereby, the unevenness | corrugation about 0.1-1.0 micrometer high can be formed in the film surface, and, thereby, appropriate slipperiness can be given to the film surface.

  The primary average particle diameter of the fine particles used in the present invention is measured by observing particles with a transmission electron microscope (magnification 500,000 to 2,000,000 times), observing 100 particles, and using the average value, the primary value is measured. The average particle size was taken.

  The apparent specific gravity of the fine particles is preferably 70 g / liter or more, more preferably 90 to 200 g / liter, and particularly preferably 100 to 200 g / liter. A larger apparent specific gravity makes it possible to make a high-concentration dispersion, which improves haze and agglomerates, and is preferable when preparing a dope having a high solid content concentration as in the present invention. Are particularly preferably used.

SiO ₂ fine particles having an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more are, for example, a mixture of vaporized silicon tetrachloride and hydrogen burned in air at 1000 to 1200 ° C. Can be obtained. For example, it is marketed by the brand name of Aerosil 200V and Aerosil R972V (above, Nippon Aerosil Co., Ltd. product), and can use them.

The apparent specific gravity described above is calculated by the following formula by measuring a weight of SiO ₂ fine particles in a graduated cylinder and measuring the weight at that time.

Apparent specific gravity (g / liter) = SiO ₂ mass (g) / SiO ₂ volume (liter)
Examples of the method for preparing the fine particle dispersion used in the present invention include the following three types.

<< Preparation Method A >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. The fine particle dispersion is added to the dope solution and stirred.

<< Preparation Method B >>
After stirring and mixing the solvent and fine particles, dispersion is performed with a disperser. This is a fine particle dispersion. Separately, a small amount of cellulose triacetate is added to the solvent and dissolved by stirring. The fine particle dispersion is added to this and stirred. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

<< Preparation Method C >>
Add a small amount of cellulose triacetate to the solvent and dissolve with stirring. Fine particles are added to this and dispersed by a disperser. This is a fine particle addition solution. The fine particle additive solution is sufficiently mixed with the dope solution using an in-line mixer.

Preparation method A is excellent in the dispersibility of SiO ₂ fine particles, and preparation method C is excellent in that the SiO ₂ fine particles are difficult to re-aggregate. Among them, the preparation method B described above is a dispersion of SiO ₂ particles, a preferred preparation method SiO ₂ particles have excellent reagglomeration hardly like, both.

《Distribution method》
The concentration of SiO ₂ when the SiO ₂ fine particles are mixed with a solvent and dispersed is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and most preferably 15 to 20% by mass. A higher dispersion concentration is preferable because liquid turbidity with respect to the added amount tends to be low, and haze and aggregates are improved.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

The addition amount of SiO ₂ fine particles to the cellulose ester relative to 100 parts by weight of cellulose ester, SiO ₂ fine particles is preferably 5.0 parts by 0.01 parts by weight, 0.05 parts by weight to 1.0 parts by weight is more Preferably, 0.1 mass part-0.5 mass part is the most preferable. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the less aggregates.

As the disperser, a normal disperser can be used. Dispersers can be broadly divided into media dispersers and medialess dispersers. For dispersion of SiO ₂ fine particles, a medialess disperser is preferred because of low haze. Examples of the media disperser include a ball mill, a sand mill, and a dyno mill. Examples of the medialess disperser include an ultrasonic type, a centrifugal type, and a high pressure type. In the present invention, a high pressure disperser is preferable. The high pressure dispersion device is a device that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. When processing with a high-pressure dispersion apparatus, for example, the maximum pressure condition inside the apparatus is preferably 9.807 MPa or more in a thin tube having a tube diameter of 1 to 2000 μm. More preferably, it is 19.613 MPa or more. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 420 kJ / hour or more are preferable.

  Examples of the high-pressure dispersing apparatus include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other manton gorin type high-pressure dispersing apparatuses such as a homogenizer manufactured by Izumi Food Machinery. And UHN-01 manufactured by Sanwa Machinery Co., Ltd.

  In addition, casting a dope containing fine particles so as to be in direct contact with the casting support is preferable because a film having high slip properties and low haze can be obtained.

  Moreover, after peeling and drying after casting and winding up into a roll, the optical thin film layer according to the present invention is provided. Until processing or shipment, packaging is usually performed in order to protect the product from dirt, static electricity, and the like. The packaging material is not particularly limited as long as the above purpose can be achieved, but a material that does not hinder volatilization of the residual solvent from the film is preferable. Specific examples include polyethylene, polyester, polypropylene, nylon, polystyrene, paper, various non-woven fabrics, and the like. Those in which the fibers are mesh cloth are more preferably used.

  The cellulose ester film used in the present invention may have a multilayer structure by a co-casting method using a plurality of dopes.

  Co-casting is a sequential multilayer casting method in which two or three layers are configured through different dies, and a simultaneous multilayer casting method in which two or three slits are combined in a die having two or three slits. Any of the multilayer casting methods combining sequential multilayer casting and simultaneous multilayer casting may be used.

  In addition, the cellulose ester used in the present invention is preferably used as a support having a small amount of bright spot foreign matter when formed into a film. In the present invention, the bright spot foreign material is a structure in which two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is arranged between them, and light from a light source is applied from one side to the other side. When the cellulose ester film is observed, the light from the light source appears to leak.

  At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used. The occurrence of bright spot foreign matter is considered to be one of the causes of unacetylated cellulose contained in the cellulose ester. As countermeasures, the use of cellulose ester with a small amount of unacetylated cellulose, It can be removed and reduced by filtering the dissolved dope solution. Further, the thinner the film thickness, the smaller the number of bright spot foreign matter per unit area, and the lower the content of cellulose ester contained in the film, the fewer bright spot foreign matter.

The bright spot foreign matter having a bright spot diameter of 0.01 mm or more is preferably 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, 50 pieces / cm ² or less, 30 pieces / cm. ² or less, preferably 10 pieces / cm ² or less, but it is particularly preferred that a 0.

Moreover, it is preferable that it is 200 pieces / cm < ² > or less also about 0.005 mm-0.01 mm bright spot, More preferably, it is 100 pieces / cm < ² > or less, 50 pieces / cm < ² > or less, 30 pieces / cm < ² > or less. The number is preferably 10 / cm ² or less, but particularly preferred is the case where the bright spot is zero. A thing with few also about a bright spot of 0.005 mm or less is preferable.

  When removing bright spot foreign matter by filtration, it is preferable to filter the composition in which a plasticizer is added and mixed, rather than filtering a cellulose ester dissolved alone, because the bright spot foreign matter removal efficiency is high. As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluororesins such as tetrafluoroethylene resin are preferably used, but ceramics, metals and the like are also preferably used. The absolute filtration accuracy is preferably 50 μm or less, more preferably 30 μm or less, and 10 μm or less, and particularly preferably 5 μm or less.

  These can also be used in combination as appropriate. The filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.

  Next, a coating layer useful for the low reflection laminate of the present invention will be described.

  The antireflection layer or other thin film of the present invention may be directly formed on the film-like or sheet-like substrate, but may be formed thereon via another layer.

  In the present invention, examples of the coating layer applied to the surface of the substrate on which the antireflection layer is formed include a clear hard coat layer, an antiglare layer, and an adhesive layer. In particular, in the case of a low reflection laminate, the clear hard coat layer is preferably provided as “other layer” in order to increase the surface hardness of the low reflection laminate. Further, as described above, a conductive layer and an overcoat layer are provided on the side on which the antireflection layer or other thin film is formed and the side opposite to the substrate.

  Here, the clear hard coat layer used for the low reflection laminate will be described as a coating layer as an “other layer” useful in the present invention.

  The clear hard coat layer is preferably a layer containing an ultraviolet curable compound (resin) that is cured by ultraviolet rays, and a low reflection laminate excellent in scratch resistance can be obtained.

  The ultraviolet curable resin layer of the clear hard coat layer is preferably a resin layer formed by polymerizing a component containing an ethylenically unsaturated monomer. Here, the ultraviolet curable resin layer refers to a layer mainly composed of a resin which is cured through a crosslinking reaction or the like by irradiation with an active ray such as an electron beam in addition to ultraviolet rays. Typical examples of the ultraviolet curable resin include an ultraviolet curable resin and an electron beam curable resin. However, a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  In general, UV-curable acrylic urethane-based resins are obtained by further reacting 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate, methacrylate) with a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. Can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, see JP-A-59-151110).

  The UV curable polyester acrylate resin can be easily obtained by reacting polyester polyol with 2-hydroxyethyl acrylate or 2-hydroxy acrylate monomer (see, for example, JP-A-59-151112). .

  Specific examples of the ultraviolet curable epoxy acrylate resin include those obtained by reacting epoxy acrylate with an oligomer, a reactive diluent and a photoinitiator added thereto (for example, JP-A-1- No. 105738). As this photoreaction initiator, one or more kinds selected from benzoin derivatives, oxime ketone derivatives, benzophenone derivatives, thioxanthone derivatives and the like can be selected and used.

  Specific examples of ultraviolet curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate. Etc. can be mentioned.

  These resins are usually used together with known photosensitizers. Moreover, the said photoinitiator can also be used as a photosensitizer. Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and the like. Further, when using an epoxy acrylate photoreactant, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photoreaction initiator or photosensitizer contained in the ultraviolet curable resin composition excluding the solvent component that volatilizes after coating and drying can be added in an amount of usually 1 to 10% by mass of the composition, and 2.5 to 6 It is preferable that it is mass%.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, benzyl acrylate, cyclohexyl acrylate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above-mentioned trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  For example, as an ultraviolet curing resin, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by Asahi Denka Kogyo Co., Ltd.) Or KOHEI HARD A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT -102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.), or Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, large Manufactured by Seika Kogyo Co., Ltd.), or KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB), or RC-5015, RC-5016, RC-5020, RC-5031, RC- 5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.) or Aulex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601 (manufactured by Sanyo Chemical Industries, Ltd.), SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.), or RCC-15C (Grace Japan Co., Ltd.) (Manufactured by company), Aronix M-6100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.) or other commercially available ones can be used.

  The ultraviolet curable resin layer can be applied by a known method.

  As a solvent for coating the ultraviolet curable resin layer, for example, it can be appropriately selected from hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or a mixture thereof can be used. . Preferably, propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether is prepared, and propylene glycol mono (alkyl group having 1 to 4 carbon atoms) alkyl ether ester is 5% by mass or more, more preferably 5 to 80% by mass. The solvent contained above is used.

As the light source for forming the cured film layer by photocuring reaction of the ultraviolet curable resin, any light source that generates ultraviolet rays can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. It can be used by using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region.

  The UV curable resin composition is applied and dried, and then irradiated with UV light from a light source. The irradiation time is preferably 0.5 seconds to 5 minutes, and 3 seconds to 2 from the curing efficiency and work efficiency of the UV curable resin. Minutes are more preferred.

  It is preferable to add inorganic or organic fine particles to the cured film layer thus obtained in order to prevent blocking and to improve scratch resistance. Examples of inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, and the like, and examples of organic fine particles include polymethacrylic acid. Methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder Polyamide-based resin powder, polyimide-based resin powder, polyfluorinated ethylene-based resin powder, and the like can be mentioned and added to the ultraviolet curable resin composition. The average particle diameter of these fine particle powders is preferably 0.005 μm to 1 μm, and particularly preferably 0.01 to 0.1 μm.

  The proportion of the ultraviolet curable resin composition and the fine particle powder is desirably blended so as to be 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition.

  The layer formed by curing the ultraviolet curable resin thus formed is a clear hard coat layer having a center line average roughness Ra of 1 to 50 nm as defined in JIS B 0601. An antiglare layer of about 1 μm may be used.

  As a method of applying the clear hard coat layer or the antiglare layer to the substrate, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater or an air doctor coater can be used. The liquid film thickness (also referred to as wet film thickness) at the time of application is about 1 to 100 μm, preferably 0.1 to 30 μm, and more preferably 0.5 to 15 μm.

(Polarizer)
The low reflection laminate according to the present invention is extremely excellent as a polarizing plate protective film. The polarizing plate can be produced by a general method. Similarly, in the present invention, a completely saponified polyvinyl alcohol aqueous solution is used on both sides of a polarizing film prepared by immersing and stretching a protective film for a polarizing plate obtained by subjecting the low reflection laminate of the present invention to alkali saponification treatment in an iodine solution. And paste them together. After making the low reflection laminate of the present invention, one side of the cellulose ester film may be saponified.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the cellulose ester film having a multilayer structure according to the present invention is bonded to form a polarizing plate. It is preferably bonded with a water-based adhesive mainly composed of completely saponified polyvinyl alcohol or the like, but the low reflection laminate according to the present invention has low moisture permeability and excellent durability.

  The image display device using the polarizing plate of the present invention is excellent in durability and can display with high contrast over a long period of time.

(Image display device)
Various image display devices can be produced by incorporating the low reflection laminate of the present invention or a polarizing plate using the same into the image display device. Examples of the image display device include a liquid crystal image display device (reflective type, transflective type, transmissive type), an organic electroluminescence element, a plasma display, and the like. For example, in the forced degradation treatment under high temperature and high humidity conditions, the low reflective laminate of the present invention or the polarizing plate using the same is also recognized for image display devices, and problems caused by the low reflective laminate are recognized. There wasn't.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the embodiments of the present invention are not limited to these examples.

  First, each coating liquid (composition) for producing a low reflection laminate was produced by the following materials and preparation methods.

<< Preparation of coating liquid >>
<Preparation of coating solution for low refractive index layer>
(Preparation of tetraethoxysilane hydrolyzate)
29 g of tetraethoxysilane and 55 g of ethanol were mixed, and after adding 16 g of a 1.6 mass% aqueous solution of acetic acid thereto, a tetraethoxysilane hydrolyzate was prepared by stirring at 25 ° C. for 20 hours.

[Low refractive index layer coating solution a: sol-gel formulation]
(Preparation of low refractive index layer composition)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 382 parts by mass Isopropyl alcohol 384 parts by mass To this mixed solvent, 226 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass was slowly added and mixed. After mixing and stirring
2 parts by mass of a 10% propylene glycol monomethyl ether solution of a linear dimethyl silicone-EO block copolymer (FZ-2207: manufactured by Nihon Unicar) was slowly added and mixed to obtain a low refractive index layer composition.

[Low refractive index layer coating solution b: hollow fine particle formulation]
(Preparation of low refractive index layer composition)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 406 parts by mass Isopropyl alcohol 408 parts by mass To this mixed solvent, 140 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass was slowly added and mixed. After mixing and stirring
Silicon dioxide fine particle dispersion (solid content 20% by mass) (P-4 manufactured by Catalytic Chemical Industry Co., Ltd.)
37 parts by mass A 10% propylene glycol monomethyl ether solution of a linear dimethyl silicone-EO block copolymer (FZ-2207: manufactured by Nihon Unicar) was slowly added and mixed to obtain a low refractive index layer composition.

[Low refractive index layer coating solution c: sol-gel / antifouling formulation]
(Preparation of low refractive index layer composition)
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 382 parts by mass Isopropyl alcohol 384 parts by mass To this mixed solvent, 226 parts by mass of tetraethoxysilane hydrolyzate was slowly added and mixed. After mixing and stirring
KBM503 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass was slowly added and mixed. After mixing and stirring
Thermally crosslinkable fluorine-containing polymer (dissolved in JN-7214 Japan Synthetic Rubber Co., Ltd. methyl isobutyl ketone, 0.6 mass% solution) 2 parts by mass was slowly added and mixed to obtain a low refractive index layer composition.

<Preparation of hard coat layer coating solution>
The following materials were stirred and mixed to obtain a hard coat layer coating solution.

Sunrad H601R (manufactured by Sanyo Chemical) 360 parts Propylene glycol monomethyl ether 320 parts Ethyl acetate 320 parts <Preparation of medium refractive index layer coating solution>
[Medium refractive index layer coating solution A]
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 2624 parts by weight Methyl ethyl ketone 874 parts by weight Isopropyl alcohol 5248 parts by weight The following proportion of water was added and stirred.

1 part by mass of water 21 parts by mass of n-tetrabutoxytitanium was slowly added to and mixed with this mixed solvent. After mixing and stirring
KBM503 (Silane coupling agent, Shin-Etsu Chemical Co., Ltd.) 24 parts by mass was slowly added and mixed. After mixing and stirring
399 parts by mass of titanium oxide fine particle dispersion (solid content: 15% by mass) (RTSPNB15WT% -G0, manufactured by CI Kasei Kogyo Co., Ltd.) was slowly added and mixed. After mixing and stirring
Dipentaerythritol hexaacrylate (KAYARAD DPHA Nippon Kayaku Co., Ltd.) 10% methyl ethyl ketone solution 534 parts by mass Irgacure 184 (Ciba Specialty Chemicals) 10% methyl ethyl ketone solution 178 parts by mass Acrylic resin (Dianar BR102, manufactured by Mitsubishi Rayon Co., Ltd.) 5% Propylene glycol monomethyl ether solution 81 parts by mass Linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Yuker Co., Ltd.) 10% propylene glycol monomethyl ether solution 16 parts by mass were sequentially added and mixed with the medium refractive index layer composition. did.

[Medium refractive index layer coating solution B]
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 2699 parts by weight Methyl ethyl ketone 900 parts by weight Isopropyl alcohol 5398 parts by weight The following proportion of water was added and stirred.

1 part by mass of water 21 parts by mass of n-tetrabutoxytitanium was slowly added to and mixed with this mixed solvent. After mixing and stirring
587 parts by mass of ITO fine particle dispersion (solid content: 20% by mass) (ELECOM V2504, manufactured by Catalyst Kasei Kogyo Co., Ltd.) was slowly added and mixed. After mixing and stirring
Dipentaerythritol hexaacrylate (KAYARAD DPHA Nippon Kayaku Co., Ltd.) 10% methyl ethyl ketone solution 285 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 10% methyl ethyl ketone solution 95 parts by mass Linear dimethyl silicone-EO block copolymer (FZ-2207 Nihonka 16 parts by mass of a 10% propylene glycol monomethyl ether solution were sequentially added and mixed to obtain a medium refractive index layer composition.

<Preparation of coating solution for high refractive index layer>
[High refractive index layer coating solution]
First, a mixed solvent was prepared in the container at the following ratio.

Propylene glycol monomethyl ether 4900 parts by mass Isopropyl alcohol 8900 parts by mass The following was sequentially added to the mixed solvent and mixed to obtain a high refractive index layer composition.

Tetra (n) butoxytitanium 310 parts by mass Terminal reactive dimethyl silicone oil (L-9000, manufactured by Nippon Unicar Co., Ltd.)
0.4 parts by mass Aminopropyltrimethoxysilane (KBE903 manufactured by Shin-Etsu Chemical Co., Ltd.)
4.8 parts by mass UV curable resin (manufactured by Asahi Denka Kogyo Co., Ltd .: KR-500) 4.6 parts by mass were sequentially added and mixed to obtain a high refractive index layer composition.

<< Preparation of hard coat layer >>
Uncoated base unwinding-coating 1 (first coater)-drying 1 (drying zone 1)-coating 2 (second coater)-drying 2 (drying zone 2)-UV irradiation-coated base winding can be performed continuously. In a test plant, the film was coated on one side of a 80 μm-thick cellulose triacetate film (Konica Minolta Opto Konicakatak KC8UX2MW, refractive index 1.49, acetyl group substitution degree 2.88) under the following conditions. A hard coat layer was produced on top.

・ Base width 180mm, coating width 150mm
・ Coating speed 10m / min
First coater: 1 slot extrusion coater Coating solution: Hard coat layer coating solution The flow rate of the coating solution was adjusted so that the film thickness after drying and curing was 6.0 μm.

・ Drying zone 1: 1m, drying temperature 80 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 80 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 80 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
<< Production of Medium Refractive Index Layer A >>
Coating base unwinding-coating 1 (first coater)-drying 1 (drying zone 1)-coating 2 (second coater)-drying 2 (drying zone 2)-UV irradiation-coated base winding can be performed continuously. In the test plant, the medium refractive index layer was produced by coating on the hard coat layer surface of the film with the hard coat layer produced as described above under the following conditions.

・ Coating speed 10m / min
First coater: 1 slot extrusion coater Coating solution: Medium refractive index layer coating solution A
The flow rate of the coating solution was adjusted so that the film thickness after drying was 70 nm.

・ Drying zone 1: 1m, drying temperature 60 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 60 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 100 ° C
-Drying zone 2-4: 2m, drying temperature 100 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
The refractive index was 1.65.

<< Production of Medium Refractive Index Layer B >>
The medium refractive index layer A was prepared in the same manner as the medium refractive index A except that the coating liquid was changed to the medium refractive index layer coating liquid B. The refractive index was 1.65.

<< Preparation of High Refractive Index Layer A >>
Coating base unwinding-coating 1 (first coater)-drying 1 (drying zone 1)-coating 2 (second coater)-drying 2 (drying zone 2)-UV irradiation-coated base winding can be performed continuously. In the test plant, the high refractive index layer A was produced by coating on the medium refractive index layer surface of the film with the medium refractive index layer A produced as described above under the following conditions.

・ Coating speed 10m / min
First coater: 1-slot extrusion coater Coating solution: High refractive index layer coating solution The flow rate of the coating solution was adjusted so that the film thickness after drying was 95 nm.

・ Drying zone 1: 1m, drying temperature 60 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 60 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 100 ° C
-Drying zone 2-4: 2m, drying temperature 100 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
The refractive index of a single layer produced on the hard coat layer under the same conditions as described above was 1.84.

<< Production of High Refractive Index Layer B >>
A high refractive index layer B was prepared in the same manner as the high refractive index layer A except that the coating base was changed to a film with a medium refractive index layer B in the preparation of the high refractive index layer A.

Example 1
Coating base unwinding-coating 1 (first coater)-drying 1 (drying zone 1)-coating 2 (second coater)-drying 2 (drying zone 2)-UV irradiation-coated base winding can be performed continuously. In the test plant, it applied on the following conditions on the hard-coat surface of the film with a hard-coat layer produced above, and produced the low-refractive-index layer.

・ Coating speed 10m / min
-1st coater: 1 slot extrusion coater Coating solution: Low refractive index layer coating solution b
The flow rate of the coating solution was adjusted so that the film thickness after drying and aging was 70 nm.

・ Drying zone 1: 1m, drying temperature 80 ℃
Second coater: 1 slot extrusion coater Coating solution: Low refractive index layer coating solution a
The flow rate of the coating solution was adjusted so that the film thickness after drying and aging was 20 nm.
・ Drying zone 2-1: 1m, drying temperature 80 ℃
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 80 ° C
-Drying zone 2-4: 2m, drying temperature 80 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
(Example 2)
Coating base unwinding-coating 1 (first coater)-drying 1 (drying zone 1)-coating 2 (second coater)-drying 2 (drying zone 2)-UV irradiation-coated base winding can be performed continuously. In the test plant, it applied on the following conditions on the hard-coat surface of the film with a hard-coat layer produced above, and produced the low-refractive-index layer.

・ Coating speed 10m / min
-1st coater: 1 slot extrusion coater Coating solution: Low refractive index layer coating solution b
The flow rate of the coating solution was adjusted so that the film thickness after drying and aging was 70 nm.

・ Drying zone 1: 1m, drying temperature 60 ℃
Second coater: 1 slot extrusion coater Coating solution: Low refractive index layer coating solution a
The flow rate of the coating solution was adjusted so that the film thickness after drying and aging was 20 nm.

・ Drying zone 2-1: 1m, drying temperature 60 ℃
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 100 ° C
-Drying zone 2-4: 2m, drying temperature 100 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
(Example 3)
The film coated with the low refractive index layer in Example 2 was heated at 70 ° C. for 6 days to perform an aging treatment.

Example 4
In Example 2, the film thickness after drying of the low refractive index layer coating liquid b of the first coater was adjusted to 85 nm, and the film thickness after drying of the low refractive index layer coating liquid a of the second coater was 5 nm. This was prepared in the same manner as in Example 2 except that the adjustment was made.

(Example 5)
In Example 2, the film thickness after drying of the low refractive index layer coating liquid b of the first coater was adjusted to 80 nm, and the film thickness after drying of the low refractive index layer coating liquid a of the second coater was 10 nm. This was prepared in the same manner as in Example 2 except that the adjustment was made.

(Example 6)
In Example 2, the film thickness after drying of the low refractive index layer coating liquid b of the first coater was adjusted to 60 nm, and the film thickness after drying of the low refractive index layer coating liquid a of the second coater was 30 nm. This was prepared in the same manner as in Example 2 except that the adjustment was made.

( Reference Example 7)
In Example 2, the film thickness after drying of the low refractive index layer coating liquid b of the first coater was adjusted to 40 nm, and the film thickness after drying of the low refractive index layer coating liquid a of the second coater was 50 nm. This was prepared in the same manner as in Example 2 except that the adjustment was made.

(Example 8)
Using the same test plant and base film as in Example 1, a low refractive index layer was produced under the following conditions.

・ Coating speed 10m / min
First coater: 2-slot extrusion coater A two-slot extrusion coater was used and wet coating was simultaneously performed by wet on wet.

  In addition, about the film thickness, it set according to the flow volume at the time of apply | coating with a single layer.

First slot: Hard coat layer side coating layer Coating solution: Low refractive index layer coating solution b
The flow rate of the coating solution was adjusted so that the film thickness after drying and aging was 70 nm.

Second slot; surface side coating layer coating solution: low refractive index layer coating solution a
The drying and flow rate of the coating solution were adjusted so that the film thickness after aging was 20 nm.

・ Drying zone 1: 1m, drying temperature 60 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 60 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 100 ° C
-Drying zone 2-4: 2m, drying temperature 100 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
Example 9
The film coated with the low refractive index layer in Example 8 was heated at 70 ° C. for 6 days to perform an aging treatment.

(Example 10)
In Example 8, the film thickness after drying of the low refractive index layer coating liquid b in the first coater first slot was adjusted to 85 nm, and after the low refractive index layer coating liquid a in the first coater second slot was dried. This was prepared in the same manner as in Example 8 except that the film thickness was adjusted to 5 nm.

(Example 11)
In Example 8, the film thickness after drying of the low refractive index layer coating liquid b in the first coater first slot was adjusted to 80 nm, and after the low refractive index layer coating liquid a in the first coater second slot was dried. This was prepared in the same manner as in Example 8 except that the film thickness was adjusted to 10 nm.

Example 12
In Example 8, the film thickness after drying of the low refractive index layer coating liquid b in the first coater first slot was adjusted to 60 nm, and the low refractive index layer coating liquid a in the first coater second slot was dried. The film was prepared in the same manner as in Example 8 except that the film thickness was adjusted to 30 nm.

( Reference Example 13)
In Example 8, the film thickness after drying of the low refractive index layer coating liquid b in the first coater first slot was adjusted to 40 nm, and after the low refractive index layer coating liquid a in the first coater second slot was dried. This was prepared in the same manner as in Example 8 except that the film thickness was adjusted to 50 nm.

(Example 14)
In Example 8, the film thickness after drying of the low refractive index layer coating liquid b in the first coater first slot was adjusted to 50 nm, and the low refractive index layer coating liquid a in the first coater second slot was dried. This was prepared in the same manner as in Example 8 except that the film thickness was adjusted to 20 nm.

(Example 15)
In Example 8, the film thickness after drying of the low refractive index layer coating liquid b in the first coater first slot was adjusted to 25 nm, and after the low refractive index layer coating liquid a in the first coater second slot was dried. This was prepared in the same manner as in Example 8 except that the film thickness was adjusted to 15 nm.

(Example 16)
In Example 8, the film thickness after drying of the low refractive index layer coating liquid b in the first coater first slot was adjusted to 70 nm, and after the low refractive index layer coating liquid a in the first coater second slot was dried. This was prepared in the same manner as in Example 8 except that the film thickness was adjusted to 50 nm.

(Example 17)
In Example 8, the film thickness after drying of the low refractive index layer coating liquid b in the first coater first slot was adjusted to 150 nm, and after the low refractive index layer coating liquid a in the first coater second slot was dried. This was prepared in the same manner as in Example 8 except that the film thickness was adjusted to 60 nm.

(Example 18)
In Example 8, a coating solution for the first coater and the second slot was prepared in the same manner as in Example 8 except that the coating solution c for the low refractive index layer was used.

(Comparative Example 1)
Coating base unwinding-coating 1 (first coater)-drying 1 (drying zone 1)-coating 2 (second coater)-drying 2 (drying zone 2)-UV irradiation-coated base winding can be performed continuously. In the test plant, it applied on the following conditions on the hard-coat surface of the film with a hard-coat layer produced above, and produced the low refractive index layer.

・ Coating speed 10m / min
First coater: 1 slot extrusion coater Coating solution: Low refractive index layer coating solution a
The flow rate of the coating solution was adjusted so that the film thickness after drying was 90 nm.

・ Drying zone 1: 1m, drying temperature 60 ℃
・ Second coater: not applied ・ Drying zone 2-1: 1 m, drying temperature 60 ° C.
-Drying zone 2-2: 2m, drying temperature 80 ° C
-Drying zone 2-3: 2m, drying temperature 100 ° C
-Drying zone 2-4: 2m, drying temperature 100 ° C
-UV irradiation after drying (Adjust the output of the UV lamp so that it becomes 120mJ / cm ² )
(Comparative Example 2)
It was produced in the same manner as in Comparative Example 1 except that the coating liquid for the first coater was changed to the low refractive index layer coating liquid b in Comparative Example 1.

(Comparative Example 3)
In Example 8, the coating solution for the hard coat layer side coating layer in the first slot was replaced with the low refractive index layer coating solution a, and the second slot; the coating solution for the surface side coating layer was replaced with the low refractive index layer coating solution b. Was prepared in the same manner as in Example 8.

(Comparative Example 4)
In Comparative Example 3, the film coated with the low refractive index layer was heated at 70 ° C. for 6 days to perform an aging treatment.

(Comparative Example 5)
In Comparative Example 3, the film thickness after drying of the low refractive index layer coating liquid a in the first coater first slot was adjusted to 80 nm, and after the low refractive index layer coating liquid b in the first coater second slot was dried. The film was prepared in the same manner as Comparative Example 3 except that the film thickness was adjusted to 10 nm.

(Comparative Example 6)
In Comparative Example 3, the film thickness after drying of the low refractive index layer coating liquid a in the first coater first slot was adjusted to 40 nm, and after the low refractive index layer coating liquid b in the first coater second slot was dried. The film was prepared in the same manner as Comparative Example 3 except that the film thickness was adjusted to 50 nm.

(Comparative Example 7)
In Comparative Example 3, the thickness after drying of the low refractive index layer coating liquid a in the first coater first slot was adjusted to 25 nm, and after drying of the low refractive index layer coating liquid b in the first coater second slot The film was prepared in the same manner as Comparative Example 3 except that the film thickness was adjusted to 15 nm.

(Comparative Example 8)
In Comparative Example 3, the thickness after drying of the low refractive index layer coating liquid a in the first coater first slot was adjusted to 150 nm, and after drying of the low refractive index layer coating liquid b in the first coater second slot The film was prepared in the same manner as Comparative Example 3 except that the film thickness was adjusted to 60 nm.

(Example 19)
It was produced in the same manner as in Example 8 except that the base film was a film coated with the high refractive index layer A in Example 8.

(Example 20)
It was produced in the same manner as in Example 8 except that the base film was changed to a film coated with the high refractive index layer B in Example 8.

( Reference Example 21)
It was produced in the same manner as in Reference Example 13 except that the base film was a film coated with the high refractive index layer A in Reference Example 13.

(Example 22)
It was produced in the same manner as in Example 15 except that the base film was changed to a film coated with the high refractive index layer A in Example 15.

(Example 23)
A film was prepared in the same manner as in Example 17 except that the base film was a film coated with the high refractive index layer A in Example 17.

(Comparative Example 9)
It was produced in the same manner as in Comparative Example 1 except that the base film in Comparative Example 1 was a film coated with the high refractive index layer A.

(Comparative Example 10)
It was produced in the same manner as in Comparative Example 2 except that the base film was a film coated with the high refractive index layer A in Comparative Example 2.

The low reflection laminated body film of the Example produced as mentioned above, Reference Examples 1-23, and Comparative Examples 1-10 was evaluated as follows.

<Evaluation>
(Measurement of refractive index and film thickness)
The refractive index and film thickness of the low refractive index layer, medium refractive index layer, and high refractive index layer are the same as the spectral reflectance of the low refractive index layer, medium refractive index layer, and high refractive index layer provided as a single layer on the hard coat layer. Obtained from the measurement results. Spectral reflectance was measured using FE-3000 (manufactured by Otsuka Electronics Co., Ltd.) after roughening the back surface of the sample and performing light absorption treatment with black spray to prevent reflection of light on the back surface. It was. The spectral reflectance was analyzed and fitted with FE-3000 software to determine the refractive index and film thickness.

(Fine particle content)
The cross section of the sample provided with the low refractive index layer was observed with a transmission electron microscope at a magnification of 200,000 times, and the fine particles in the low refractive index layer were observed. The boundary surface between the substrate side layer and the surface side layer is applied to the low refractive index layer in the electron microscope image according to the ratio determined from the design film thickness of the substrate side layer and the surface side layer. Were determined. By this observation, the number a of particles having a center on the substrate side from the boundary surface and the number b of particles having a center on the surface side were counted.

  The content (%) of fine particles was calculated from the number of each particle according to the following formula.

Fine particle content on the substrate side A = a / (a + b)
Surface side fine particle content B = b / (a + b)
(Scratch resistance)
Place the sample on a smooth table, apply a load of 200 g per cm ² on # 0000 steel wool, rub the sample surface (low reflective laminate side) 10 times, and range 1 cm in the direction perpendicular to the rubbing direction. The number of scratches generated in step 1 was visually counted.

(crack)
The low reflection laminate film is placed in a thermostat at 100 ° C. and held for 400 hours, and then a black tape is applied to the back surface of the antireflection treatment surface, and the antireflection treatment surface is observed with a microscope (objective lens 20 ×, eyepiece 10 ×). Then, the occurrence of cracks was visually evaluated as follows.

○: No crack △: Weak, short crack occurs ×: Long crack occurs (Adhesion)
Using a cutter on the side of the low-reflection laminate of the sample, 11 scratches of 1 mm in length and width are placed one by one to make 100 squares of 1 mm square (cross cut), and tape (cellophane tape No. 29 made by Nitto Denko) is placed on it. After applying and rubbing 10 times with a spatula, peel off the tape vigorously. This operation was repeated three times to see the degree of film peeling.

◎: No film peeling ○: There is a very small amount of peeling △: There is a small amount of peeling ×: There is a large peeling (reflectance)
Using a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.), after roughening the back surface of the sample on the low-reflection laminate side, light absorption treatment is performed with a black spray to reflect light on the back surface. Then, the reflection spectrum in the visible light region (380 nm to 780 nm) was measured under the condition of regular reflection at 5 degrees. From the measurement result of this reflection spectrum, based on JIS-Z-8701 and CIE1931, the Y value in a C light source and a 2 degree visual field was made into the reflectance.

  The above evaluation results are shown in Table 1 below.

From Table 1, Examples 1 to 6, 8 to 12, 14 to 20, 22, and 23 of the present invention have sufficiently low reflectance with respect to Comparative Examples 1 to 10, and excellent scratch resistance and crack resistance. It is clear that it has adhesiveness.

  Moreover, it turns out that adhesiveness is excellent when apply | coating by wet on wet.

Claims (5)

A composite particle having at least two low-refractive index layers on a base material, wherein at least the base-side layer of the low-refractive index layer has fine particles as a porous particle and a coating layer provided on the surface of the porous particle; Alternatively, it contains hollow particles filled with a solvent, gas, or porous substance inside, the fine particle content and film thickness of the layer on the base material side are A and a, respectively, and the surface side layer is a solution of an alkoxysilicon compound. A silicon dioxide matrix using a hydrolyzate obtained by decomposition and condensation of an alkoxysilicon compound, wherein the following formulas I and II are satisfied when the fine particle content and film thickness of the surface-side layer are B and b, respectively: A low-reflection laminate characterized by the above.
Formula IA> B> 0
Formula II a ≧ b 2. The low reflection laminate according to claim 1, wherein the total thickness of the low refractive index layers is 50 to 200 nm. The low reflective laminated body of Claim 1 or 2 which has at least 1 layer chosen from a medium refractive index layer and a high refractive index layer in the base material side rather than a low refractive index layer. In producing a low reflective laminate having at least two low refractive index layers on a substrate, composite particles having porous particles and a coating layer provided on the surface of the porous particles, or a solvent, gas inside, Alternatively, after applying a low refractive index layer containing hollow particles filled with a porous material, a low refractive index layer containing an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing an alkoxysilicon compound is applied to a sol-gel reaction. A method for producing a low-reflection laminate, comprising: laminating by: On the low-refractive index layer containing composite particles having porous particles and a coating layer provided on the surface of the porous particles, or hollow particles filled with a solvent, gas, or porous substance inside, the alkoxysilicon The method for producing a low reflection laminate according to claim 4, wherein a low refractive index layer containing an alkoxysilicon compound hydrolyzate obtained by hydrolyzing and condensing a compound is laminated on a wet on wet basis.