JP3955971B2 - Base material with antireflection film - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention includes a resin base material, a hard coat film formed on the base material, and an antireflection film formed on the hard coat film.
More specifically, the present invention relates to a substrate with an antireflection film that is excellent in scratch resistance, transparency, haze, etc. even though a resin substrate is used because a hard coat film containing inorganic particles is provided. .
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
In order to prevent reflection on the surface of a substrate such as glass or plastic sheet, it is known to form an antireflection film on the surface, for example, fluororesin, fluoride, etc. by coating, vapor deposition, CVD, etc. A film of a material having a low refractive index such as magnesium is formed on the surface of glass or plastic.
[0003]
Also known is a method of forming an antireflection coating by applying a coating liquid containing low refractive index fine particles such as silica fine particles to the surface of a substrate. Furthermore, a method is also known in which a coating liquid containing silica particles is applied to the surface of a substrate to form an antireflection coating having fine and uniform irregularities with silica particles.
Furthermore, the present inventors have proposed to use a sol in which low refractive index composite oxide fine particles in which the surface of porous fine particles is coated with silica are dispersed as the above-mentioned low refractive index fine particles (Japanese Unexamined Patent Publication No. Hei. 7-133105).
[0004]
However, in the conventional method described above, particularly when the substrate is a resin substrate, the scratch resistance is insufficient. For this reason, a hard coat film is provided between the base material and the antireflection coating, but although the scratch resistance is improved to some extent, it is not necessarily sufficient, and it has excellent strength. It is desired.
Moreover, when the refractive index of the base material is low, sufficient antireflection performance may not be obtained because the difference between the refractive index of the base material and the refractive index of the antireflection coating is small.
[0005]
For this reason, the appearance of a substrate with an antireflection film that is excellent in scratch resistance, transparency, haze, and the like has been desired.
[0006]
OBJECT OF THE INVENTION
The present invention is a base material with an antireflection film comprising a resin base material, a hard coat film and an antireflection film sequentially formed on the base material, and has excellent scratch resistance, transparency, haze, and the like. It aims at providing the base material with a prevention film.
[0007]
SUMMARY OF THE INVENTION
In order to solve the problems associated with the prior art, the present inventors diligently studied, and as a result, the inorganic particles were blended into the hard coat film, and the hard coat film thickness and the particle size of the inorganic particles had a specific relationship. As a result, it was found that the scratch resistance and film strength of the film were remarkably improved, and the present invention was completed.
[0008]
That is, the base material with an antireflection film according to the present invention is
A resin substrate, a hard coat film containing inorganic particles and a film-forming matrix formed on the resin substrate, and an antireflection film formed on the hard coat film, and an average particle diameter of the inorganic particles The ratio (Dp / Th) between (Dp) and the thickness (Th) of the hard coat film is in the range of 0.2 to 1.0.
[0009]
The film forming matrix is preferably a resin matrix.
The average particle diameter of the inorganic particles is in the range of 0.2 to 20 μm, and the thickness of the hard coat film is in the range of 1 to 20 μm (however, the average particle diameter of the inorganic particles is the thickness of the hard coat film). The content of inorganic particles in the hard coat film is preferably in the range of 0.1 to 90% by weight.
[0010]
The refractive index difference between the refractive index of the inorganic particles and the refractive index of the film forming matrix is preferably 0.2 or less.
The hard coat film may further contain colored particles having an average particle size in the range of 5 to 200 nm.
In the present invention, the base material may have a refractive index of 1.55 or less, and an intermediate film having a refractive index of 1.6 or more may be provided between the hard coat film and the antireflection film.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the base material with an antireflection film according to the present invention will be described.
Base material with antireflection film
The base material with an antireflection film of the present invention comprises a resin base material, a hard coat film containing inorganic particles formed on the resin base material, and an antireflection film formed on the hard coat film,
The ratio (Dp / Th) between the average particle diameter (Dp) of the inorganic particles and the thickness (Th) of the hard coat film is in the range of 0.2 to 1.0.
[0012]
Resin base material
As a base material used for this invention, it consists of resin materials, such as a polycarbonate, an acrylic resin, PET, and TAC, and the thing of shapes, such as a plastic panel, a plastic panel, etc., is used.
Hard coat film
The hard coat film used in the present invention contains inorganic particles and a film forming matrix.
[0013]
(i) Inorganic particles
As inorganic particles, SiO₂, Al₂O_ThreeTiO₂, ZrO₂, SiO₂・ Al₂O_Three, SiO₂・ ZrO₂Such as oxide, composite oxide, oxide whose surface is coated with resin, composite oxide,
Colloidal metal particles such as gold, silver and platinum,
Carbon materials such as carbon black and graphite,
What consists of inorganic compounds, such as magnesium fluoride and sodium aluminum fluoride, is used.
[0014]
The shape of the inorganic particles is not particularly limited, but spherical particles are suitable because they can be densely arranged in a base material.
Among these, SiO₂, SiO₂・ Al₂O_Three, SiO₂・ ZrO₂Silica-based particles such as these are suitable because it is easy to obtain true spherical particles, and therefore a hard coat film having excellent adhesion between the hard coat film and the substrate can be formed.
[0015]
Moreover, in order to improve the dispersibility with respect to resin mentioned later, the surface of the inorganic particles may be treated with a silane coupling agent.
The average particle size of such inorganic particles is not particularly limited as long as the relationship with the thickness of the hard coat film described later satisfies a specific relationship, and is usually 0.2 to 20 μm, and more preferably 1 to What is in the range of 10 micrometers is suitable.
[0016]
When the average particle diameter of the inorganic particles is less than the lower limit of the above range, the dispersibility of the inorganic particles is reduced, or the particles are too small with respect to the thickness of the hard coat film, so that the finally obtained reflection with a hard coat film There is a tendency that the strength of the prevention film becomes insufficient. Further, if the average particle diameter exceeds the upper limit of the above range, the adhesion with the matrix for forming the hard coat film is lowered, cracks are likely to occur, and if the thickness is larger than the thickness of the hard coat film, the hard coat film is formed. Unevenness may remain on the surface of the antireflection film formed on the film, and the surface hardness may become uneven.
[0017]
(ii) Matrix for film formation
The hard coat film may contain a layer forming component from the viewpoints of adhesion to the substrate and coating properties. A resin matrix is suitable as such a layer forming component.
As such a resin matrix, specifically, any of known thermosetting resins and thermoplastic resins can be employed as coating resins, and specifically, conventionally used polyester resins. , Polycarbonate resin, polyamide resin, polyphenylene oxide resin, thermoplastic acrylic resin, vinyl chloride resin, fluorine resin, vinyl acetate resin, silicone rubber and other thermoplastic resins, urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone Examples thereof include thermosetting resins such as resins, phenol resins, epoxy resins, unsaturated polyester resins, and thermosetting acrylic resins. Further, two or more kinds of copolymers or modified products of these resins may be used.
[0018]
These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.
In the present invention, in particular, a thermosetting resin or an ultraviolet curing type is preferable because a substrate with an antireflection film having a high pencil hardness can be obtained even if the amount of the oxide particles is small.
[0019]
(iii) Hard coat film
The thickness (Th) of the hard coat film is not particularly limited, but in the present invention, the ratio of the average particle diameter (Dp) of the inorganic particles to the thickness (Th) of the hard coat film to be formed ( It is desirable that Dp / Th) is in the range of 0.2 to 1.0, preferably 0.5 to 0.98.
[0020]
When the ratio (Dp / Th) is less than the lower limit, the effect of improving the adhesion to the substrate may be insufficient, and the hardness (pencil hardness) of the obtained substrate with an antireflection film is further improved. Effect may be insufficient. Further, if the ratio (Dp / Th) exceeds the upper limit, irregularities may be formed on the surface of the antireflection film. For this reason, hardness (pencil hardness) and wear resistance may decrease, Since the film thickness becomes non-uniform, appearance villages may occur or the antireflection performance may deteriorate.
[0021]
When the ratio (Dp / Th) is within the above range, the inorganic particles are arranged in a single layer or about two layers in the hard coat film, so that the adhesion between the hard coat film and the substrate is enhanced.
The content of inorganic particles in the hard coat film is preferably in the range of 0.1 to 90% by weight, more preferably 2 to 50% by weight. When the content of the inorganic particles in the hard coat film is less than the lower limit, since the content of the inorganic particles is small, the effect of including the inorganic particles, that is, the adhesion with the base material, the (pencil) hardness, and the strength The effect of improving may not be obtained. If the content of oxide particles in the hard coat film exceeds the above upper limit, the hard coat film formation matrix is small, so the adhesion to the substrate is reduced, voids are generated, and the strength of the hard coat film is reduced. Sometimes.
[0022]
The thickness of the hard coat film is not particularly limited as long as the relationship with the inorganic particles is within the above range, but it is preferably 1 to 20 μm, more preferably 2 to 10 μm.
However, the average particle diameter of the inorganic particles does not exceed the thickness of the hard coat film.
When the thickness of the hard coat film is less than the lower limit of the above range, since the hard coat film is thin, the stress applied to the antireflection film surface cannot be sufficiently absorbed, resulting in insufficient pencil hardness. There is. When the upper limit of the range is exceeded, it becomes difficult to apply a uniform layer thickness or to dry uniformly. For this reason, the strength and transparency of the antireflection film obtained by the generation of cracks and voids. May be insufficient.
[0023]
In the case of creating a transparent hard coat film, among the above-mentioned inorganic particles, if silica-based particles are used, these particles have a low refractive index, and thus a component for forming a hard coat film (for forming a hard coat film) The difference in refractive index from the refractive index of the matrix) can be reduced, and a substrate with an antireflection film excellent in transparency and haze can be obtained. As such silica-based particles, specifically, silica-based particles, organopolysiloxane-based particles and the like disclosed in JP-A Nos. 63-2110016 and 11-228699 can be suitably used. . The organopolysiloxane-based particles contain organic groups in the particles, and therefore have good dispersibility in the resin described later used as a matrix for forming a hard coat film, and thus a hard coat film having excellent adhesion can be formed. When a transparent hard coat film is prepared, the refractive index difference between the refractive index of the hard coat film forming matrix, the refractive index of the inorganic particles, and the refractive index of the hard coat film forming matrix is 0.2 or less. Further, it is preferably 0.1 or less. When the difference in refractive index exceeds 0.2, visible light scattering becomes significant, and the transparency of the hard coat film and the finally obtained antireflection film may be lowered.
[0024]
When transparency is not required as the hard coat film, among the above-described inorganic particles, for example, a colored one such as a metal colloid or a carbon material may be used.
Furthermore, when transparency is not requested | required, the average particle diameter may contain the colored particle of the range of 5-200 nm and also 10-100 nm with the inorganic particle.
Colored particles include organic pigments such as phthalocyanine and bitumen, inorganic pigments such as zinc oxide, white lead, lead tan, lead suboxide, titanium oxide, alumina, calcium carbonate, magnesium carbonate, barium carbonate, and barium sulfate, as well as carbon. Examples thereof include colored particles such as particles, metal colloid particles such as gold, silver, and platinum. It is difficult to obtain particles having an average particle diameter of less than 5 nm, and it may be difficult to adjust the light shielding property (blind function) of the obtained antireflection film-coated substrate depending on the kind of the colored particles. When the average particle diameter exceeds 200 nm, the scattering of visible light becomes remarkable, and the transparency of the film may be lowered.
[0025]
The content of the colored particles in the hard coat film is preferably in the range of 0.1 to 20% by weight, more preferably 0.2 to 10% by weight.
When the content of the colored particles in the hard coat film is less than 0.1% by weight, the light shielding property described above becomes insufficient, and when it exceeds 20% by weight, the light shielding property is too strong and the transparency tends to be lowered. It is in. In addition, when using a colored particle, it is preferable to use it so that the total content of an above described inorganic particle and a colored particle may be in the range of 1 to 90 weight%.
[0026]
Further, if necessary, the hard coat film may contain particles made of high hardness polystyrene, polycarbonate, or the like together with inorganic particles. Such particles made of polystyrene or polycarbonate can be blended in the hard coat film without being used in combination with inorganic particles.
Such a hard coat film can be formed by applying a coating solution containing a matrix forming component for forming a hard coat film and optional components such as inorganic particles and colored particles.
[0027]
In addition, the coating solution may contain a solvent that can dissolve the matrix-forming component and easily volatilize. If the matrix-forming component is a thermosetting resin, a curing agent is blended as necessary. can do.
In the case of a thermoplastic resin, such a coating solution is applied to a substrate by a known method such as a dipping method, a spray method, a spinner method, or a roll coating method, dried, and cured in the case of a thermosetting resin. If necessary, a hard coat film can be formed by heat treatment at a temperature lower than the softening point of the substrate.
[0028]
Anti-reflection coating
The antireflection film used in the present invention is not particularly limited as long as it has antireflection performance, and a conventionally known antireflection film can be used. Specifically, an antireflection performance is provided if the refractive index is lower than that of the hard coat film.
Such an antireflection film comprises an antireflection film forming matrix and, if necessary, a low refractive index component.
[0029]
The matrix for forming an antireflection film is a component that can form a film on the surface of a substrate such as a hard coat film (or an intermediate film to be described later), and is suitable for conditions such as adhesion to the substrate and hardness coatability. It can be used by selecting from the resin to be used, and the same coating resin as the matrix for forming the hard coat film can be used.
As a low refractive index component, CaF₂, NaF, NaAlF₆In addition to low refractive index substances such as MgF, silica-based particles (silica particles, silica hollow particles, silica / alumina composite oxide particles), porous silica-based particles, and the like can be given.
[0030]
For example, when composite oxide fine particles in which the surface of porous inorganic oxide fine particles disclosed in JP-A-7-133105 filed by the applicant of the present application is coated with silica are used, the refractive index is low and the reflection is excellent in antireflection performance. A prevention film can be obtained.
On the other hand, it is also possible to use a hydrolyzable organosilicon compound as a matrix. Specifically, for example, a partial hydrolyzate of alkoxysilane obtained by adding water and an acid or alkali as a catalyst to a mixture of alkoxysilane and alcohol is preferably used.
[0031]
The hydrolyzable organosilicon compound includes a general formula R_nSi (OR)_4-nAn alkoxysilane represented by [R, R ′: a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, an acrylic group, etc., n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.
[0032]
The content of the low refractive index component in the antireflection film is preferably 90% by weight or less, more preferably 50% by weight or less. If the content of the low refractive index component exceeds 90% by weight, the strength of the coating film and the adhesion to a substrate such as a hard coat film (or an intermediate film described later) may be insufficient, resulting in lack of practicality.
The thickness of the antireflection film is preferably 50 to 300 nm, more preferably 80 to 200 nm.
[0033]
When the thickness of the antireflection film is less than 50 nm, the strength of the film, the antireflection performance, etc. may be inferior. If the thickness of the antireflective film exceeds 300 nm, cracks may occur in the film, resulting in a decrease in film strength, and the film may be too thick, resulting in insufficient antireflection performance.
The refractive index of such an antireflective film varies depending on the mixing ratio of the low refractive index component and the resin matrix, and the refractive index of the resin used, but is usually in the range of 1.28 to 1.50. preferable. If the refractive index of the antireflection film exceeds 1.50, although depending on the refractive index of the substrate, the antireflection performance may be insufficient, and it is difficult to obtain a film having a refractive index of less than 1.28. is there.
[0034]
The antireflection film is formed by applying an antireflection film forming coating solution containing the above-described forming matrix and, if necessary, a low refractive index component and a solvent.
The solvent used is not particularly limited as long as it easily evaporates and does not adversely affect the obtained antireflection film.
The coating solution for forming the antireflection film is not particularly limited, and is applied to the substrate by a known method such as a dipping method, a spray method, a spinner method, or a roll coating method, as in the case of forming the hard coat film. It may be applied and dried. In particular, when the forming component is a thermosetting resin, curing of the hard coat film may be promoted by heat treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, etc. When the decomposable organosilicon compound is contained, the hydrolysis and polycondensation of the hydrolyzable organosilicon compound may be promoted by heat treatment.
[0035]
In the present invention, an intermediate film may be provided between the hard coat film and the antireflection film.
Interlayer film
An intermediate film having a refractive index of 1.6 or more is formed.
In particular, when the refractive index of the substrate is 1.55 or less, the difference from the refractive index of the antireflection film is small, and the antireflection performance may be insufficient. For this reason, the refractive index is 1.6 or more. An intermediate film is preferably formed.
[0036]
In addition, when a coloring component is contained in the hard coat film, it is not always necessary to provide an intermediate film.
The intermediate film is composed of metal oxide fine particles having a high refractive index and, if necessary, an intermediate film forming matrix.
The matrix for forming an intermediate film refers to a component that can form an intermediate film on the surface of the hard coat film, and it is used by selecting from a resin or the like suitable for conditions such as adhesion to the hard coat film and coatability. Specifically, paint resins, hydrolyzable organosilicon compounds such as alkoxysilanes exemplified in the antireflection film, and the like can be used in the same manner as the matrix for forming the hard coat film.
[0037]
As the metal oxide fine particles having a high refractive index, metal oxide particles having a refractive index of 1.60 or more are preferably used. A more preferable refractive index is 1.70 or more. As such metal oxide fine particles, titanium oxide (2.50), zinc oxide (2.0), zirconium oxide (2.20), cerium oxide (2.2), tin oxide (2.0), Thallium oxide (2.1), barium titanate (2.40), aluminum oxide (1.73), magnesium oxide (1.77), yttrium oxide (1.92), antimony oxide (2.0), oxidation And indium (2.0). (Refractive index in parentheses)
Among these, conductive fine particles such as titanium oxide, cerium oxide, tin oxide, antimony oxide, zirconium oxide, and indium oxide, and further conductive particles obtained by doping these fine particles with different elements such as antimony, tin, and fluorine, The obtained base material with an antireflection film is preferable because it has an antistatic effect in addition to the antireflection performance.
[0038]
When the refractive index of the metal oxide particles is less than 1.60, the refractive index of the obtained intermediate film is not 1.60 or more, and the difference in refractive index from the antireflection film is small, resulting in insufficient antireflection performance. The effect of providing the intermediate film may not be sufficiently obtained.
The average particle size of the metal oxide fine particles is preferably in the range of 5 to 100 nm. A more preferable range is 10 to 60 nm. It is difficult to obtain particles having an average particle diameter of less than 5 nm. When the average particle diameter exceeds 100 nm, the scattering of visible light becomes remarkable, and the transparency of the film may be lowered.
[0039]
The content of the metal oxide particles in the intermediate film is not particularly limited as long as an intermediate film having a refractive index of 1.6 or more is obtained, and varies depending on the matrix for forming the intermediate film and the refractive index of the metal oxide particles. Usually, it is preferably 30 to 100% by weight, more preferably 50 to 95% by weight. (Note that the intermediate film does not include a matrix and may be composed of a single metal oxide particle)
When the content of the metal oxide particles in the intermediate film is less than 30% by weight, the refractive index of the intermediate film does not become 1.60 or more depending on the type of the metal oxide particles, and the effect of providing the intermediate film is obtained. It may not be possible.
[0040]
Such an intermediate film is formed by applying an intermediate film forming coating solution containing metal oxide fine particles having a high refractive index, and an intermediate film forming matrix and a solvent as required. When preparing a coating solution for forming an intermediate film using metal oxide fine particles, it is preferably used as a sol in which metal oxide fine particles are dispersed in a dispersion medium, and an organic solvent such as a water-dispersed sol or alcohol. The organic solvent-dispersed sol dispersed in the organic solvent, or after treating the fine particles with a known coupling agent, the organic solvent-dispersed sol dispersed in the organic solvent and the coating resin are diluted with an appropriate organic solvent to obtain an intermediate film It can be set as the coating liquid for formation. Further, a surfactant or the like can be added to the coating solution in order to improve dispersibility, stability and the like.
[0041]
The solvent used is not particularly limited as long as it easily evaporates and does not adversely affect the obtained antireflection film and intermediate film.
The coating method for the coating solution for forming an intermediate film is not particularly limited, as in the case of the coating solution for forming an antireflective film. Like the coating solution for forming a hard coat film, a dipping method or a spraying method is used. It may be applied to a substrate by a known method such as a method, a spinner method, or a roll coating method, and dried, particularly when the forming component is a thermosetting resin, by heat treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, Hardening of the hard coat film may be promoted, and when the hydrolyzable organosilicon compound is included in the forming component, the hydrolysis / polycondensation of the hydrolyzable organosilicon compound is promoted by heat treatment. Also good.
[0042]
When forming the intermediate film in this way, first, after forming the above-mentioned hard coat film on the base material, apply the coating liquid for forming the intermediate film, then dry, and further, if necessary, the softening point of the base material Heat treatment may be performed at a temperature lower than that, and then the above-described antireflection film may be formed.
[0043]
【The invention's effect】
In the present invention, since a hard coat film containing inorganic particles is provided on the surface of the resin base material, it is excellent in scratch resistance, transparency, haze, etc. even though the resin base material is used. A base material with an antireflection film is obtained.
[0044]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[0045]
[Preparation example]
[Production of composite oxide fine particle dispersed sol]
27.4 g of methylmethoxysilane was mixed with 872.6 g of a 0.65% strength by weight aqueous sodium hydroxide solution and stirred at room temperature for 1 hour._ThreeSiO_3/2A 1.5% by weight colorless and transparent partial hydrolyzate was prepared.
[0046]
Then, the average particle diameter as seed particles is 5 nm, SiO.₂A mixture of 20 g of silica sol having a concentration of 20% by weight and 380 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor is 10.5, and the mother liquor contains SiO.₂900 g of 1.5% by weight sodium silicate aqueous solution, 900 g of the aqueous solution of the partial hydrolyzate, Al₂O_ThreeAs a solution, 1800 g of a sodium aluminate aqueous solution having a concentration of 0.5% by weight was simultaneously added over 6 hours. Meanwhile, the temperature of the reaction mother liquor was maintained at 80 ° C. The pH of the reaction mother liquor rose to 12.7 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution is cooled to room temperature, washed with an ultrafiltration membrane, and a methyl group-containing SiO2 having a solid content concentration of 20% by weight.₂・ Al₂O_ThreeA dispersion of composite oxide fine particles (A-1) was obtained.
[0047]
Next, 550 g of pure water was added to 250 g of the dispersion of composite oxide fine particles (A-1) and heated to 98 ° C., and the sodium silicate aqueous solution was dealkalized with a cation exchange resin while maintaining this temperature. Silicic acid solution (SiO₂(Concentration of 3.5% by weight) 1,000 g was added over 5 hours, and the silica-coated methyl group-containing SiO₂・ Al₂A dispersion of O3 composite oxide fine particles (B-1) was obtained. Subsequently, 1125 g of pure water was added to 500 g of a dispersion having a solid content of 13% by weight, which was washed with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35.5% by weight) was added dropwise to adjust the pH to 1.0. Then, a treatment for removing aluminum from the fine particles was performed.
[0048]
Next, while adding 10 L of hydrochloric acid aqueous solution of pH 3.0 and 5 L of pure water, the dissolved aluminum salt is washed and removed using an ultrafiltration membrane, and concentrated and coated with silica having a solid content concentration of 13% by weight. SiO₂・ Al₂O_ThreeA dispersion of composite oxide fine particles (C-1) was obtained.
Next, a mixture of 1500 g of the composite oxide fine particle (C-1) dispersion, 500 g of pure water, 1,750 g of ethanol and 626 g of ammonia water having a concentration of 28% by weight was heated to 35 ° C., and then ethyl silicate ( SiO₂104 g) was added and coated with the silica. This is concentrated to 5% by weight of solid content with an evaporator, adjusted to pH 10 by adding ammonia water with a concentration of 15% by weight, heated at 180 ° C. for 2 hours in an autoclave, and then concentrated with an ultrafiltration membrane to obtain solid content. Methyl group-containing SiO completely coated with 10% by weight silica₂・ Al₂O_ThreeA dispersion of composite oxide fine particles (D-1) was obtained.
[0049]
This silica-coated composite oxide fine particle (D-1)₂/ Al₂O_ThreeThe molar ratio was 278, the average particle size was 34 nm, and the refractive index was 1.36.
The refractive index of the particles was measured as follows.
(1) A dispersion of the composite oxide fine particles (D-1) is taken in an evaporator and the dispersion medium is evaporated.
(2) This is dried at 120 ° C. to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid (paste) becomes transparent is used as the refractive index of the fine particles.
[0050]
[Example 1]
Hard coat film forming coating solution ( H-1 Preparation of
Silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .; true sphere SW, average particle diameter of 4 μm) were used as inorganic particles, and 55.55 g of a silica particle ethanol dispersion having a concentration of 20 wt% dispersed in ethanol was prepared. 100 g of acrylic resin (Hitaroid 1007, manufactured by Hitachi Chemical Co., Ltd., refractive index 1.49) and 400 g of a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol were sufficiently mixed to form a hard coat film. Coating solution (H-1) was prepared.
[0051]
Coating liquid for antireflection film formation (R-1) Preparation of
The dispersion liquid of the composite oxide fine particles (D-1) obtained in the above preparation example was passed through an ultrafiltration membrane, and water in the dispersion medium was replaced with ethanol. 50 g of this ethanol sol (solid content concentration 5% by weight), 3 g of UV curable resin (Dainippon Ink Co., Ltd .: Unidic V5500, refractive index 1.50) and 1/1 (weight ratio of isopropanol and n-butanol) ) 47 g of the mixed solvent was thoroughly mixed to prepare an antireflection film-forming coating solution (R-1).
[Manufacture of base material with antireflection film (F-1)]
The hard coat film-forming coating solution (H-1) was applied to a PET film (thickness: 188 μm, refractive index: 1.65) by a bar coater method, and dried at 80 ° C. for 1 minute. At this time, the thickness of the hard coat film was 5 μm.
[0052]
Next, an antireflection film-forming coating solution (R-1) is applied by a bar coater method, dried at 80 ° C. for 1 minute, and then cured by irradiation with a high-pressure mercury lamp (80 W / cm) for 1 minute to prevent reflection. A substrate with film (F-1) was prepared. At this time, the thickness of the antireflection film was 80 nm.
Table 1 shows the total light transmittance, haze, reflectance of light having a wavelength of 550 nm, and refractive index of the coating of the obtained base material with antireflection film (F-1) and uncoated PET film (F-0). Show. The total light transmittance and haze were measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the reflectance was measured by a spectrophotometer (JASCO Corporation, Ubest-55). The refractive indexes of the hard coat film and the antireflection film were determined by applying each of the above coating liquids individually to a silicon wafer in the same manner as described above, drying and heat treatment, and using an ellipsometer (EMS-1 manufactured by ULVAC). It was measured.
[0053]
Adhesion
The surface of the base with antireflection film (F-1) is made with 11 parallel scratches with a knife at intervals of 1 mm in length and width to make 100 squares, and cellophane tape (R) is adhered to it, and then cellophane. Adhesion was evaluated by classifying the number of squares that remained without peeling off the film when the tape was peeled into the following four stages. The results are shown in Table 1.
[0054]
Number of remaining cells: 95 or more: ◎
Number of remaining squares 90-94: ○
Number of remaining squares: 85-89:
Number of remaining squares: 84 or less: ×
Pencil hardness measurement
It measured with the pencil hardness tester according to JIS-K-5400.
[0055]
Measurement of scratch resistance
(Using # 0000 steel wool, load 500g / cm²The film surface was visually observed, evaluated according to the following criteria, and the results are shown in Table 1.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
[0056]
[Example 2]
Hard coat film forming coating solution ( H-2 Preparation of
Silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .; true sphere SW, average particle size 4 μm) were used as inorganic particles, and 55.55 g of a silica particle ethanol dispersion having a concentration of 20% by weight dispersed in ethanol was prepared. 100 g of urethane-based UV curable resin (Dainippon Ink Co., Ltd .: Unidic V5500) and 400 g of a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol were mixed thoroughly to form a hard coat film. A coating solution (H-2) was prepared.
[0057]
Coating liquid for intermediate film formation ( M-1 Preparation of
Titanium oxide colloid (manufactured by Catalyst Kasei Kogyo Co., Ltd .; Optolake 1130Z, refractive index 2.2, average particle diameter 20 nm, concentration 20% by weight) 20 g as high refractive index particles, and UV curable resin (Dainippon Ink Co., Ltd. Manufactured by: Unidic V5500, refractive index 1.50) 0.44 g and isopropanol 6.7 g were sufficiently mixed to prepare a coating solution (M-1) for forming an intermediate film.
[Manufacture of base material with antireflection film (F-2)]
The coating liquid for forming a hard coat film (H-2) was applied to a PET film (thickness: 188 μm, refractive index: 1.65) by a bar coater method, dried at 80 ° C. for 1 minute, and then subjected to a high-pressure mercury lamp (80 W / Cm) for 1 minute to cure. At this time, the thickness of the hard coat film was 5 μm.
[0058]
Subsequently, the coating liquid for forming an intermediate film (M-1) was applied by a bar coater method and dried at 80 ° C. for 1 minute. At this time, the thickness of the intermediate film was 80 nm. The refractive index was 1.80.
Next, in the same manner as in Example 1, an antireflection film-forming coating solution (R-1) was applied by a bar coater method, dried at 80 ° C. for 1 minute, and irradiated with ultraviolet rays to form an antireflection film-coated substrate (F -2) was prepared. At this time, the thickness of the antireflection film was 80 nm.
[0059]
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-2). The refractive index of the intermediate coating was measured with an ellipsometer (EMS-1 manufactured by ULVAC) by applying the intermediate coating forming coating solution (M-1) to a silicon wafer in the same manner as described above, drying and heating treatment. . Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0060]
[Example 3]
Hard coat film forming coating solution ( H-3 Preparation of
Silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .; true sphere SW, average particle diameter of 4 μm) were used as inorganic particles, and 277.8 g of a silica particle ethanol dispersion liquid having a concentration of 20 wt% dispersed in ethanol was prepared. To this, 55.5 g of an ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidic V5500, refractive index 1.50) and 222.2 g of a mixed solvent of isopropanol and n-butanol in 1/1 (weight ratio) were sufficiently added. By mixing, a coating liquid for forming a hard coat film (H-3) was prepared.
[Manufacture of base material with antireflection film (F-3)]
A hard coat film was formed in the same manner as in Example 2 except that the coating liquid for forming a hard coat film (H-3) was used. At this time, the thickness of the hard coat film was 5 μm.
[0061]
Subsequently, in the same manner as in Example 2, an intermediate coating and an antireflection film were formed to obtain a substrate with antireflection film (F-3).
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-3). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0062]
[Example 4]
Hard coat film forming coating solution ( H-4 Preparation of
Silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .; true sphere SW, average particle diameter of 8 μm) were used as inorganic particles, and 277.8 g of a silica particle ethanol dispersion liquid having a concentration of 20 wt% dispersed in ethanol was prepared. A hard coat film was prepared by thoroughly mixing 55.5 g of an ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidic V5500) and 222.2 g of a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol. A forming coating solution (H-4) was prepared.
[Manufacture of base material with antireflection film (F-4)]
A hard coat film was formed in the same manner as in Example 2 except that the coating liquid for forming a hard coat film (H-4) was used. At this time, the thickness of the hard coat film was 10 μm.
[0063]
Subsequently, in the same manner as in Example 2, an intermediate coating and an antireflection film were formed to obtain a substrate with antireflection film (F-4).
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-4). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0064]
[Example 5]
Hard coat film forming coating solution ( H-5 Preparation of
Silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .; true sphere SW, average particle size 1.5 μm) were used as inorganic particles, and 167.7 g of silica particle ethanol dispersion liquid having a concentration of 20 wt% dispersed in ethanol was prepared. did. To this was sufficiently 77.7 g of an ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidic V5500, refractive index 1.50) and 311.1 g of a mixed solvent of 1/1 (weight ratio) of isopropanol and n-butanol. By mixing, a coating liquid for forming a hard coat film (H-5) was prepared.
[Manufacture of base material with antireflection film (F-5)]
A hard coat film was formed in the same manner as in Example 2 except that the coating liquid for forming a hard coat film (H-5) was used and applied to a PET film (thickness: 100 μm, refractive index: 1.65). . At this time, the thickness of the hard coat film was 2 μm.
[0065]
Subsequently, in the same manner as in Example 2, an intermediate coating and an antireflection film were formed to obtain a base material with antireflection film (F-5).
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-5). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0066]
[Example 6]
Hard coat film forming coating solution ( H-6 Preparation of
Silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .; true sphere SW, average particle diameter of 4 μm) were used as inorganic particles, and 167.7 g of a silica particle ethanol dispersion liquid having a concentration of 20% by weight dispersed in ethanol was prepared. To this was sufficiently 77.7 g of an ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidic V5500, refractive index 1.50) and 311.1 g of a mixed solvent of 1/1 (weight ratio) of isopropanol and n-butanol. By mixing, a coating liquid for forming a hard coat film (H-6) was prepared.
[0067]
Coating liquid for intermediate film formation ( M-2 Preparation of
Preparation of metal oxide particles(ITO)
A solution obtained by dissolving 79.9 g of indium nitrate in 686 g of water and a solution obtained by dissolving 12.7 g of potassium stannate in a potassium hydroxide solution having a concentration of 10% by weight were prepared. Was added to 1000 g of pure water maintained at 50 ° C. over 2 hours. During this time, the pH in the system was maintained at 11. The Sn-doped indium oxide hydrate dispersion was filtered and washed from the obtained Sn-doped indium oxide hydrate dispersion, dried, then calcined in air at a temperature of 350 ° C. for 3 hours, and further 600 in air. By baking at a temperature of 2 ° C. for 2 hours, Sn-doped indium oxide fine particles were obtained. The Sn-doped indium oxide fine particles were dispersed in pure water so as to have a concentration of 30% by weight, and further adjusted to pH 3.5 with an aqueous nitric acid solution. Then, this mixture was maintained at 30 ° C. with a sand mill. A sol was prepared by grinding for a period of time. Next, this sol was treated with an ion exchange resin to remove nitrate ions, and pure water was added to prepare a conductive metal oxide particle-dispersed sol having a concentration of 20% by weight. (At this time, the average particle diameter was 50 nm and the refractive index was 1.80.)
20 g of the above conductive metal oxide particle-dispersed sol, 0.44 g of an ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidic V5500) and 6.7 g of isopropanol are sufficiently mixed to form a coating solution for forming an intermediate film ( M-2) was prepared.
[Manufacture of base material with antireflection film (F-6)]
A hard coat film was formed in the same manner as in Example 2 except that the hard coat film forming coating solution (H-6) was used. At this time, the thickness of the hard coat film was 5 μm.
[0068]
Thereafter, a substrate with antireflection film (F-6) was obtained in the same manner as in Example 2 except that the coating solution for forming an intermediate coating (M-2) was used. At this time, the thickness of the intermediate layer was 120 nm.
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-5). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0069]
[Example 7]
Hard coat film forming coating solution ( H-7 Preparation of
Silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .; true sphere SW, average particle diameter of 4 μm) were used as inorganic particles, and 167.7 g of a silica particle ethanol dispersion liquid having a concentration of 20% by weight dispersed in ethanol was prepared. 77.7 g of acrylic resin (Hitaroid 1007, manufactured by Hitachi Chemical Co., Ltd., refractive index 1.49) and 311.1 g of a 1: 1 (weight ratio) mixed solvent of isopropanol and n-butanol were mixed thoroughly. A coating liquid for forming a hard coat film (H-7) was prepared.
[0070]
Coating liquid for intermediate film formation ( M-3 Preparation of
Ethyl silicate (SiO₂A small amount of hydrochloric acid was added to a mixed solution of 20 g (concentration 28 wt%), ethanol 45 g and pure water 5.33 g to obtain a matrix containing a partial hydrolyzate of ethyl silicate. This was thoroughly mixed with 252 g of a conductive metal oxide particle-dispersed sol having a concentration of 20% by weight obtained in the same manner as in Example 6 to prepare a coating liquid (M-3) for forming an intermediate film.
[0071]
Coating liquid for antireflection film formation (R-2) Preparation of
Ethyl silicate (SiO₂A small amount of hydrochloric acid was added to a mixed solution of 20 g (concentration 28 wt%), ethanol 45 g and pure water 5.33 g to obtain a matrix containing a partial hydrolyzate of ethyl silicate. To this, 74.6 g of ethanol sol (solid content concentration 5% by weight) of the composite oxide fine particles (D-1) obtained in the same manner as in Example 1 was sufficiently mixed to form a coating solution for forming an antireflection film ( R-2) was prepared.
[Manufacture of base material with antireflection film (F-7)]
The coating solution for forming a hard coat film (H-7) was applied to an acrylic plate (Mitsubishi Rayon Co., Ltd .: acrylite, refractive index 1.49) by a bar coater method, and dried at 80 ° C. for 1 minute. At this time, the thickness of the hard coat film was 5 μm.
[0072]
Next, a coating solution (M-3) for forming an intermediate film was applied by a bar coater method, and then dried at 80 ° C. for 30 minutes. At this time, the thickness of the intermediate film was 100 nm.
Next, after applying the coating solution (R-2) for forming an antireflection film by the bar coater method, drying at 80 ° C. for 30 minutes, and heat-treating at 120 ° C. for 30 minutes, the substrate with antireflection film (F− 7) was prepared. At this time, the thickness of the antireflection film was 80 nm.
[0073]
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-7). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0074]
[Example 8]
Preparation of oxide particles
A solution (solution A) in which 8 g of methyltrimethoxysilane and 8 g of tetramethoxysilane were dissolved in 350 g of ethanol was prepared. On the other hand, a mixed solution (liquid B) of 6 g of pure water, 78 g of 28% ammonia water and 350 g of ethanol was prepared.
[0075]
The liquid A and the liquid B were mixed and stirred at 25 ° C. for 3 hours to hydrolyze / condense the alkoxysilane. Further, 3.3 g of a 1% by weight potassium hydroxide aqueous solution was added, and sonication was further performed for 10 minutes to stabilize the seed. At this time, the pH was 12. The average particle size of the seed particles in this seed particle dispersion was 0.15 μm as a result of measurement by a centrifugal particle size distribution measurement method.
[0076]
The seed particle dispersion was heated and concentrated until the obtained seed particle dispersion became 160 g, and then alkali and ammonia were removed using 10 cc of cation exchange resin. To this seed particle dispersion, 5000 g of pure water and 250 g of butanol were added. The seed particle dispersion thus diluted is cooled to 0 ° C., and while maintaining this temperature, a mixed solution of 400 g of methyltrimethoxysilane and 100 g of vinyltrimethoxysilane is added to this seed particle dispersion at 0.005 g / pure water— While dropping at an addition rate of g · hour, an aqueous ammonia solution having a concentration of 0.028% was added at an addition rate of about 0.012 / pure water-g · hour, and the pH of the seed particle dispersion was 8.0. The seed particles were grown by hydrolyzing and condensing methyltrimethoxysilane and vinyltrimethoxysilane on the seed particles. Then, after stirring at 20 ° C. for 2 hours, the mixture was further heated to 80 ° C. and aged for 5 hours.
[0077]
The obtained fine particles were separated from the liquid, dried, and then heated at 220 ° C. while supplying air with a relative humidity of 60% to obtain organopolysiloxane fine particles.
The obtained fine particles contained an organic group and contained 19% by weight as carbon. The average particle size was 7.6 μm, the 10% compression modulus was 205 Kgf / mm 2, and the particle size variation coefficient was 1.8%.
[0078]
Hard coat film forming coating solution ( H-8 Preparation of
Using the above-mentioned organopolysiloxane fine particles as inorganic particles and dispersing them in ethanol, 167.7 g of a silica particle ethanol dispersion having a concentration of 20% by weight was prepared. 77.8 g of ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidic V5500, refractive index 1.50) and 311 g of a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol were sufficiently mixed with this. Thus, a coating solution for forming a hard coat film (H-8) was prepared.
[Manufacture of base material with antireflection film (F-8)]
The hard coat film forming coating solution (H-8) was applied to an acrylic plate (Mitsubishi Rayon Co., Ltd .: acrylite, refractive index 1.49) by a bar coater method and dried at 80 ° C. for 1 minute. It was cured by irradiation with a high pressure mercury lamp (80 W / cm) for 1 minute. At this time, the thickness of the hard coat film was 10 μm.
[0079]
Thereafter, an intermediate film and an antireflection film were formed in the same manner as in Example 7 to prepare a base material with antireflection film (F-8).
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-8). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0080]
[Example 9]
Hard coat film forming coating solution ( H-9 Preparation of
SiO as inorganic particles₂・ ZrO₂Using particles (Catalyst Kasei Kogyo Co., Ltd .: P-1500K, average particle diameter of 5 μm, refractive index of 1.49), 167.7 g of silica particle ethanol dispersion having a concentration of 20% by weight dispersed in ethanol was prepared. did. Thoroughly mix 134.2 g of acrylic resin (Hitaroid 1007, manufactured by Hitachi Chemical Co., Ltd., refractive index 1.49) and 537.3 g of a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol. A coating liquid for forming a hard coat film (H-9) was prepared.
[Manufacture of base material with antireflection film (F-9)]
The coating liquid for forming a hard coat film (H-9) was applied to an acrylic plate (Mitsubishi Rayon Co., Ltd .: acrylite, refractive index 1.49) by a bar coater method and dried at 80 ° C. for 1 minute. At this time, the thickness of the hard coat film was 10 μm.
[0081]
Thereafter, an intermediate film and an antireflection film were formed in the same manner as in Example 7 to prepare a base material with antireflection film (F-9).
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-9). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0082]
[Example 10]
Hard coat film forming coating solution ( H-10 Preparation of
SiO as inorganic particles₂・ ZrO₂35 g of particles (Catalyst Kasei Kogyo Co., Ltd .: P-1500K, average particle size 5 μm, refractive index 1.49) are dispersed in 140 g of water, and 2 g of γ-glycidoxypropyltrimethoxysilane is used as a silane coupling agent. And stirred at 60 ° C. for 1 hour. Next, 167.7 g of an ethanol dispersion of silica / zirconore particles having a concentration of 20 wt% dispersed in ethanol after solvent substitution was prepared. Thoroughly mix 134.2 g of acrylic resin (Hitaroid 1007, manufactured by Hitachi Chemical Co., Ltd., refractive index 1.49) and 537.3 g of a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol. A coating liquid for forming a hard coat film (H-10) was prepared.
[Manufacture of base material with antireflection film (F-10)]
The coating solution for forming a hard coat film (H-10) was applied to an acrylic plate (Mitsubishi Rayon Co., Ltd .: acrylite, refractive index 1.49) by a bar coater method and dried at 80 ° C. for 1 minute. At this time, the thickness of the hard coat film was 10 μm.
[0083]
Thereafter, an intermediate film and an antireflection film were formed in the same manner as in Example 7 to prepare a base material with antireflection film (F-10).
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-10). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0084]
Example 11
Hard coat film forming coating solution ( H-11 Preparation of
Silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .; true sphere SW, average particle diameter of 4 μm) were used as inorganic particles, and 50 g of a silica particle ethanol dispersion having a concentration of 20% by weight dispersed in ethanol was prepared.
[0085]
Using platinum particles (Tokuroku Main Store Co., Ltd .: TPT-200, average particle size 0.1 μm, spherical black particles) as colored particles, and 100 g of a platinum particle ethanol dispersion liquid having a concentration of 20 wt% dispersed in ethanol. Prepared.
70 g of ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidic V5500) and 280 g of a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol were sufficiently mixed with this, and a coating solution for forming a hard coat film (H-11) was prepared.
[Manufacture of base material with antireflection film (F-11)]
The coating liquid for forming a hard coat film (H-11) was applied to a PET film (thickness: 188 μm, refractive index: 1.65) by a bar coater method, and dried at 80 ° C. for 1 minute. At this time, the thickness of the hard coat film was 5 μm.
[0086]
Thereafter, an intermediate film and an antireflection film were formed in the same manner as in Example 7 to prepare a base material with antireflection film (F-11).
The table shows the total light transmittance, haze, reflectance, and refractive index of each coating film of the obtained base material with antireflection film (F-11). Also, adhesion, pencil hardness, and scratch resistance were measured, and the results are shown in Table 1.
[0087]
[Comparative Example 1]
Hard coat film forming coating solution ( RH-1) Preparation of
100 g of acrylic resin (Hitaroid 1007, manufactured by Hitachi Chemical Co., Ltd., refractive index 1.49) and 400 g of a 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol are sufficiently mixed to form a hard coat film. A liquid (RH-1) was prepared.
[Manufacture of base material with antireflection film (RF-1)]
A substrate with antireflection film (RF-1) was prepared in the same manner as in Example 1 except that the coating liquid for forming a hard coat film (RH-1) was used. At this time, the thickness of the hard coat film was 5 μm.
[0088]
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating of the obtained base material with antireflection film (RF-1). Further, adhesion, pencil height, and scratch resistance were measured, and the results are shown in Table 1.
[0089]
[Comparative Example 2]
Hard coat film forming coating solution ( RH-2 Preparation of
Hard coat film by thoroughly mixing 100 g of UV curable resin (Dainippon Ink Co., Ltd .: Unidic V5500, refractive index 1.50) and 400 g of 1/1 (weight ratio) mixed solvent of isopropanol and n-butanol. A forming coating solution (RH-2) was prepared.
[Manufacture of base material with antireflection film (RF-2)]
A substrate with antireflection film (RF-2) was prepared in the same manner as in Example 2 except that the hard coat film forming coating solution (RH-2) was used. At this time, the thickness of the hard coat film was 5 μm.
[0090]
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating of the obtained base material with antireflection film (RF-2). Further, adhesion, pencil height, and scratch resistance were measured, and the results are shown in Table 1.
[0091]
[Comparative Example 3]
[Manufacture of base material with antireflection film (RF-3)]
A hard coat film-forming coating solution (RH-1) obtained in the same manner as in Comparative Example 1 was applied to an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd .: acrylite, refractive index 1.49) by a bar coater method. Dried for 1 minute at ° C. At this time, the thickness of the hard coat film was 5 μm.
[0092]
Thereafter, a substrate with antireflection film (RF-3) was prepared in the same manner as in Example 7. At this time, the thickness of the hard coat film was 5 μm.
Table 1 shows the total light transmittance, haze, reflectance, and refractive index of each coating of the obtained base material with antireflection film (RF-3). Further, adhesion, pencil height, and scratch resistance were measured, and the results are shown in Table 1.
[0093]
[Table 1]

Claims (4)

A resin substrate, a hard coat film containing inorganic particles and a film-forming matrix formed on the resin substrate, and an antireflection film formed on the hard coat film, and an average particle diameter of the inorganic particles The ratio (Dp / Th) between (Dp) and the thickness (Th) of the hard coat film is in the range of 0.2 to 1.0 ,
Refractive index difference between the refractive index of the film-forming matrix of the inorganic particles is at 0.2 or less,
Refractive index of the substrate 1. Is 55 or less, the refractive index between the hard coat film and the antireflection film has a 1. 6 or more intermediate layer,
The intermediate film is an inorganic oxide selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, cerium oxide, tin oxide, thallium oxide, barium titanate, aluminum oxide, magnesium oxide, yttrium oxide, antimony oxide, and indium oxide. Particles, or conductive fine particles doped with different elements of antimony, tin, and fluorine in these fine particles,
A substrate with an antireflection film, wherein the haze as a whole substrate is in the range of 0.2 to 3.5 .   The base material with an antireflection film according to claim 1, wherein the film forming matrix is a resin matrix.   The average particle diameter of the inorganic particles is in the range of 0.2 to 20 μm, and the thickness of the hard coat film is in the range of 1 to 20 μm (however, the average particle diameter of the inorganic particles exceeds the thickness of the hard coat film) The substrate with an antireflection film according to claim 1 or 2, wherein the content of the inorganic particles in the hard coat film is in the range of 0.1 to 90% by weight.   The substrate with an antireflection film according to any one of claims 1 to 3, wherein the hard coat film further contains colored particles having an average particle diameter in the range of 5 to 200 nm.