JP2008163205A - Coating for forming transparent coating film and substrate with transparent coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating for forming a transparent coating film which can form a transparent coating film excellent in adhesiveness with a substrate, strength, antireflection properties and anti-glare properties, and to provide a substrate with a transparent coating film. <P>SOLUTION: The coating for forming a transparent coating film comprises a low refractive index particulate and a high refractive index particulate in which the affinity with a matrix-forming component differs to each other, a polymerization initiator, and a solvent. Both the low refractive index particulate and the high refractive index particulate are surface-treated with a silane coupling agent. The surface-treated low refractive index particulate (A) has a refractive index (n<SB>A</SB>) of 1.20-1.45. The surface-treated high refractive index particulate (B) has a refractive index (n<SB>B</SB>) which is higher than (n<SB>A</SB>). The concentration of the low refractive index particulate (A) is 0.1-10 wt.% as a solid content. The concentration of the high refractive index particulate (B) is 0.1-10 wt.% as a solid content. The concentration of the matrix-forming component as a solid content is 1-30 wt.%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel transparent film-forming paint and a substrate with a transparent film formed using the transparent film-forming paint.

  Conventionally, it has been known to form an antireflection film on the surface of the substrate in order to prevent reflection on the surface of the substrate such as glass, plastic sheet, and plastic lens. For example, coating method, vapor deposition method, CVD method, etc. To form a film of a low refractive index substance such as fluororesin or magnesium fluoride on the surface of a glass or plastic substrate, or apply a coating solution containing low refractive index fine particles such as silica fine particles to the substrate surface. Thus, a method for forming an antireflection coating is known (see, for example, JP-A-7-133105). At this time, in order to improve the antireflection performance, it is also known to form a high refractive index film containing fine particles of high refractive index under the antireflection coating.

Furthermore, in the display device or the like, it is also known to form irregularities on the surface in order to provide string-proofing properties (sometimes referred to as anti-glare properties). (JP 2002-169001 A, JP 2002-71904 A, JP 2001-281411 A, JP 2001-34350 A)
However, in the conventional method of forming a multilayer film, it is necessary to perform a process of applying a paint, drying, and curing as necessary for each paint. There was a problem in performance and economy.

In addition, the inventors of the present application use a coating solution containing two kinds of fine particles, which are different in average particle size and different in conductive particle having a small particle size and low refractive index fine particle having a large particle size in Japanese Patent Application Laid-Open No. 2003-12965. Therefore, it has been proposed that a conductive coating excellent in antireflection performance can be formed by a single application. However, in this method, the fine particle layer may not be formed in a form in which two kinds of fine particles are completely separated from each other in addition to the fact that there is no string-proof performance, so the contrast in the light place is low. Was insufficient.
JP-A-7-133105 JP 2002-169001 A JP 2002-71904 A JP 2001-281411 A JP 2001-34350 A In Japanese Patent Application Laid-Open No. 2003-12965

  Under such circumstances, by applying and drying a coating for forming a transparent film once, it has excellent adhesion to the base material, strength, etc., as well as excellent antireflection performance and stringproof performance, as well as productivity and economy. In addition, it is desired to provide a coating material for forming a transparent film and a substrate with a transparent film capable of forming an excellent transparent film.

As a result of intensive studies in view of such problems, the present inventors applied a coating containing two kinds of particles having different affinity to the matrix-forming component and having different average particle diameters, and then dried the coating in the film. The two kinds of particles are separated from each other, that is, the surface-treated fine particles are unevenly distributed in the upper part of the transparent film, the surface-treated relatively large particles are unevenly distributed in the lower part of the transparent film, and the surface of the film is uneven. As a result, the present invention has been completed.
[1] A transparent film-forming paint comprising a low-refractive index fine particle and a high-refractive index fine particle having different affinity for a matrix-forming component, a matrix-forming component, a polymerization initiator, and a solvent,
Both low refractive index fine particles and high refractive index fine particles are surface treated with a silane coupling agent, and the refractive index (n _A ) of the surface treated low refractive index fine particles ( _A ) is in the range of 1.20 to 1.45. The average particle diameter is in the range of 5 to 200 nm, the surface charge (Q _A ) is in the range of 5 to 80 μeq / g,
The refractive index (n _B ) of the surface-treated high refractive index fine particles (B) is higher than (n _A ), and the average particle size is 0.5
In the range of -5 μm, the surface charge (Q _B ) is in the range of 25-100 μeq / g, and the concentration of the low refractive index fine particles (A) is in the range of 0.1-10 wt% as the solid content, Transparent, characterized in that the concentration of the high refractive index fine particles (B) is in the range of 0.1 to 10% by weight as the solid content, and the concentration of the matrix forming component as the solid content is in the range of 1 to 30% by weight. Film-forming paint.
[2] The surface charge of the low-refractive index fine particles _(A) (Q A) and the surface charge amount of the high屈率fine particles (B) the difference between _{(Q B) (Q B)} - (Q A) is 20 The transparent film-forming paint of [1] in the range of ~ 95 μeq / g.
[3] The matrix-forming component comprises a hydrophilic matrix-forming component and a hydrophobic matrix-forming component, and the concentration of the hydrophilic matrix-forming component as a solid content (C _MA ) and the concentration of the hydrophobic matrix-forming component as a solid content (C _MB) and concentration ratio of _{(C MA) / (C MB} ) is in the range of 0.01 to 1 [1] or [2] of the transparent film-forming coating.
[4] The polyfunctional (meth) acrylic compound, wherein the hydrophilic matrix-forming component is an organosilicon compound represented by the following formula (1) or a hydrolyzate, hydrolyzed polycondensate and / or a hydrophilic functional group thereof: Acid ester resin,
SiX ₄ (1)
(However, in the formula, X represents an alkoxy group having 1 to 4 carbon atoms, a silanol group, halogen, or hydrogen.)
Polyfunctional (meth) acrylic ester resin in which the hydrophobic matrix forming component has an organosilicon compound represented by the following formula (2) or a hydrolyzate, hydrolyzed polycondensate and / or a hydrophobic functional group thereof The paint for forming a transparent film according to [3].
_{R n -SiX 4-n (2} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 1 to 3)
[5] The hydrophilic functional group is one or more selected from a hydroxyl group, an amino group, a carboxyl group, a sulfo group, and a glycidyl group, and the hydrophobic functional group is a (meth) acryloyl group, an alkyl group, a phenyl group, The paint for forming a transparent film according to [3] or [4], which is at least one selected from a urethane group and a CF ₂ group.
[6] The solvent is a mixed solvent of a solvent (A) having a boiling point of 50 to 100 ° C. and a solvent (B) having a boiling point of more than 100 ° C. to 200 ° C., and the solvent (A) in the mixed solvent The coating composition for forming a transparent film according to [1] to [5], wherein the ratio of the solvent (B) is in the range of 10 to 50% by weight.
[7] A substrate with a transparent coating in which a transparent coating having irregularities on the surface is formed on the substrate, the low refractive index fine particles (A) with the transparent coating surface-treated and the high refractive index with the surface treatment It consists of fine particles (B) and a matrix component, and the surface-treated low refractive index fine particles (A) are unevenly distributed in a layer on the upper part of the transparent film, and the surface-treated high refractive index fine particles (B) are on the lower part of the transparent film. It is unevenly distributed and the average film thickness of the transparent film is in the range of 1 to 10 μm,
A substrate with a transparent coating, wherein the difference between the average height of convex portions (T _convex ) of the transparent coating and the average height of concave portions (T _concave ) (T _convex )-(T _concave ) is in the range of 30 to 1500 nm.
[8] The refractive index (n _A ) of the surface-treated low refractive index fine particles (A) in the transparent film is in the range of 1.20 to 1.45, the average particle diameter is in the range of 5 to 200 nm, and the surface Treated high refractive index fine particles (B)
The refractive index (n _B ) is higher than (n _A ), the average particle diameter is in the range of 0.5 to 5 μm, and the content of the surface-treated low refractive index fine particles (A) is 1 to 30 in terms of solid content. The substrate with a transparent coating according to [7], wherein the content of the surface-treated high refractive index fine particles (B) is in the range of 5% by weight to 70% by weight as the solid content.
[9] The matrix component comprises a hydrophilic matrix component and a hydrophobic matrix component, and the content of the hydrophilic matrix component as a solid (W _MA ) and the content of the hydrophobic matrix component as a solid (W _MB) ) And a transparent coating-coated substrate according to [7] or [8], wherein the concentration ratio (W _MA ) / (W _MB ) is in the range of 0.01 to 1.
[10] The hydrophilic matrix component is a polyfunctional (meth) acrylic acid ester resin having a hydrolytic polycondensate of an organosilicon compound represented by the following formula (1) and / or a hydrophilic functional group,
SiX ₄ (3)
(Where X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen)
The hydrophobic matrix component is a polyfunctional (meth) acrylate resin having a hydrolytic polycondensate and / or a hydrophobic functional group of an organosilicon compound represented by the following formula (4): 9] A substrate with a transparent coating.
R _n -SiX _4-n (4)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 1 to 3)
[11] The hydrophilic functional group is at least one selected from a hydroxyl group, an amino group, a carboxyl group, a sulfo group, and a glycidyl group, and the hydrophobic functional group is a (meth) acryloyl group, an alkyl group, a phenyl group, A substrate with a transparent coating, which is at least one selected from a urethane group and a CF ₂ group.

  According to the present invention, a coating for forming a transparent film is applied once and dried, thereby being excellent in adhesion to the base material, strength, etc., and excellent in antireflection performance and stringproof performance, and also in productivity and economy. A transparent film-forming coating material capable of forming an excellent transparent film and a substrate with a transparent film formed using the transparent film-forming coating material can be provided. The obtained substrate with a transparent coating can be suitably used for a display screen such as an LCD display, a plasma display, a projection display, an EL display, or a CRT display.

Hereinafter, first, the transparent film-forming paint according to the present invention will be specifically described.
Transparent film-forming paint The transparent film-forming paint according to the present invention comprises low refractive index fine particles, high refractive index fine particles, matrix forming components, a polymerization initiator, and a solvent, which have different affinity to the matrix forming component.
Low Refractive Index Fine Particles The low refractive index fine particles (A) surface-treated with a silane coupling agent are used in the present invention.

  As the low refractive index fine particles, silica-based fine particles having cavities inside according to Japanese Patent Application Laid-Open Nos. 2001-233611 and 2003-192994 filed by the applicant of the present application have a low refractive index and are fine particles in a colloidal region. Therefore, it can be suitably employed.

The average particle diameter of the low refractive index fine particles is preferably 5 to 200 nm, more preferably 10 to 100 nm, and the refractive index is preferably 1.15 to 1.40.
The low refractive index fine particles are surface-treated with a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltrie Toxisilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxy Ethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltrioxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meta ) Acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (Meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane Orchid, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3- Ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyl Methyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercap Trimethoxysilane, trimethyl silanol, methyl trichlorosilane, and the like.

In the surface treatment, for example, a predetermined amount of the above-described silane coupling agent is added to an alcohol dispersion of silica-based fine particles, water is added thereto, and an acid or alkali is added as a catalyst for hydrolysis of the silane coupling agent as necessary. To hydrolyze the silane coupling agent. Subsequently, an organic solvent dispersion of the low refractive index fine particles (A) subjected to surface treatment can be obtained by substituting with an organic solvent. As an organic solvent, it is preferable to use the solvent mentioned later.

The amount ratio of the low refractive index fine particles to the silane coupling agent (weight as the solid content of the silane coupling agent / weight of the low refractive index fine particles) varies depending on the average particle diameter of the low refractive index fine particles. It is preferable that it exists in the range of 05-1 further 0.1-0.5. If the weight ratio is small, the dispersibility and stability in the solvent are low, the stability of the paint becomes insufficient, the low refractive index fine particles are aggregated in the paint, and the film is whitened when the film is formed. Or the adhesion to the substrate and the hardness of the coating film may be insufficient. When the weight ratio is large, the hydrophobicity becomes too high (the surface charge amount is 5 μq / g or less), and the low refractive index fine particles (A) surface-treated in the paint are different depending on the type of matrix forming component used. The film may agglomerate and a uniform layer may not be formed on the upper part of the film. Further, when the film is formed, the film may be whitened or the hardness of the film may be insufficient. In addition, since there are many surface treatment agents having a higher refractive index than low refractive index fine particles, the refractive index of the surface-treated low refractive index fine particles (A) is increased, the refractive index of the resulting transparent coating is increased, and antireflection performance, Contrast and the like may not be improved.

The average particle diameter of the surface-treated low refractive index fine particles (A) is 5 to 200 nm, more preferably 10 to 10
It is preferably in the range of 0 nm.
When the average particle size of the surface-treated low refractive index fine particles (A) is less than 5 nm, the average particle size is 5 n.
It is difficult to obtain low refractive index fine particles of less than m, and even if obtained, the refractive index of the low refractive index fine particles may exceed 1.40. It is difficult to obtain the following particles.
If the average particle diameter of the surface-treated low refractive index fine particles (A) exceeds 200 nm, unnecessary irregularities may be formed on the surface of the transparent coating, and the haze value of the transparent coating may increase.

The refractive index (n _A ) of the surface-treated low refractive index fine particles (A) is preferably in the range of 1.20 to 1.45, more preferably 1.20 to 1.35. It is difficult to obtain a material having a low refractive index (n _A ) exceeding the lower limit of this range. If the refractive index (n _A ) is larger than this range, the anti-reflection performance will be insufficient depending on the refractive index of the base material or the lower layer film. It may be insufficient.

The surface-treated low refractive index fine particles (A) preferably have a surface charge (Q _A ) in the range of 5 to 80 μeq / g, more preferably 7 to 70 μeq / g. When the surface charge (Q _A ) is small, the low-refractive-index fine particles (A) surface-treated in the paint may aggregate because the hydrophobicity is too high, and a uniform layer is not formed on the top of the film. There is. If the surface charge (Q _A ) is too high,
When the film is formed, the surface-treated low refractive index fine particles (A) are not unevenly distributed in the upper layer and tend to be dispersed in the film.

  The surface charge of the surface-treated low refractive index fine particles (A) can be measured by using a surface potential titration device (Mutek Co., Ltd. pcd-03) and dispersing the fine particle dispersion to 0.001 N poly-diallyldimethyl chloride. Titration with ammonium can be carried out as the surface charge per μg of particle (μeq / g).

The concentration of the surface-treated low refractive index fine particles (A) in the paint for forming a transparent film is 0.1 as a solid content.
It is preferably in the range of ˜10% by weight, more preferably 0.2 to 5% by weight, especially 0.5 to 3.0% by weight.

When the concentration of the surface-treated low refractive index fine particles (A) is low, a transparent coating with a low refractive index cannot be obtained, and the reflectance of the transparent coating increases, resulting in insufficient antireflection performance and poor contrast in bright places. May be sufficient. When the concentration of the surface-treated low refractive index fine particles (A) is high, the total solid content concentration of the paint also increases, so that the coating property is lowered and it becomes difficult to form a uniform transparent film, or the surface smoothness is low. It may disappear or voids may be formed inside the transparent film, causing light scattering, and the haze value of the transparent film may be increased, and the scratch resistance may be insufficient.

High refractive index fine particles In the present invention, high refractive index fine particles surface-treated with a silane coupling agent are used.
As the high refractive index fine particles, fine particles having a refractive index of 1.46 or more can be used, but usually fine particles having a refractive index of 1.65 or more are preferably used, for example, ZrO ₂ , TiO ₂ , Sb _2. Examples thereof include fine particles such as O ₅ , ZnO ₂ , Al ₂ O ₃ , SnO ₂ , ZrO ₂ —SiO ₂ , antimony-doped oxide, tin-doped indium oxide, and phosphorus-doped tin oxide (PTO).

Since fine particles such as Sb ₂ O ₅ , antimony-doped tin oxide, tin-doped indium oxide, and phosphorus-doped tin oxide have electrical conductivity, a transparent film having antistatic performance can be obtained.

The average particle diameter of the high refractive index fine particles is preferably in the range of 0.5 to 5 μm, more preferably 1 to 3 μm.
The high refractive index fine particles are surface-treated with a silane coupling agent. As the silane coupling agent, the same silane coupling agent as that used for the low refractive index fine particles can be used. The surface treatment of the high refractive index fine particles (B) is performed by, for example, adding a predetermined amount of a silane coupling agent to an alcohol dispersion of fine particles such as titanium oxide, adding water thereto, and hydrolyzing the silane coupling agent as necessary. An acid or alkali is added as a catalyst for the hydrolysis to hydrolyze the silane coupling agent. Subsequently, the organic solvent dispersion liquid of the high refractive index fine particles (B) subjected to surface treatment can be obtained by substituting with an organic solvent. As an organic solvent, it is preferable to use the solvent mentioned later.

  The amount ratio of the high refractive index fine particles to the silane coupling agent (weight as the solid content of the silane coupling agent / weight of the high refractive index fine particles) varies depending on the average particle diameter of the high refractive index fine particles. It is preferably in the range of 005 to 0.2, more preferably 0.01 to 0.1.

  When the weight ratio is less than 0.005, the affinity with the resin in the paint is low, the paint stability is insufficient, the high refractive index fine particles agglomerate in the paint, and the surface has regular irregularities. May not be formed.

  When the weight ratio is more than 0.2, although depending on the type of matrix forming component used, the refractive index of the high refractive index particles decreases or the hydrophobicity becomes too high (the surface charge amount is 25 μq / g or less). In some cases, it may not be unevenly distributed under the transparent film, and regular irregularities may not be formed on the surface.

The silane coupling agent treatment of the high refractive index fine particles is performed in the same manner as the silane coupling agent treatment of the low refractive index fine particles, but the surface charge amount (Q _B ) of the surface treated high refractive index fine particles ( _B ) is The type and amount of the silane coupling agent are set so that the difference (Q _B ) − (Q _A ) from the surface charge amount (Q _A ) described later falls within the predetermined range and the refractive index falls within the range described later. Select as appropriate.

The average particle diameter of the surface-treated high refractive index fine particles (B) is 0.5 to 5 μm, more preferably 1 to 3 μm.
It is preferable that it exists in the range.
When the average particle diameter of the surface-treated high refractive index fine particles (B) is less than 0.5 μm, the difference between the height of the convex portion (T _convex ) and the height of the concave portion (T _concave ) (T _convex) )-(T- _concave ) may be less than 30 nm, and sufficient stringproof performance may not be obtained.
When the average particle diameter of the high refractive index fine particles surface-treated (B) is more than 5 [mu] m, height of the convex portion of the transparent film (T _convex) and recess height (T _concave) difference between the (T _convex) - ( (T- _concave ) may exceed 1.5 μm, and in this case, sufficient string-proof performance may not be obtained.

The refractive index (n _B ) of the surface-treated high refractive index fine particles (B) is not particularly limited as long as it is higher than the refractive index (n _A ) of the surface-treated low refractive index fine particles, but the refractive index difference (n _B ) -(N _A ) is preferably 0.2 or more, more preferably in the range of 0.3 to 1.6. When the difference in refractive index is less than 0.2, the effect of improving the antireflection performance is insufficient, and when the difference in refractive index exceeds 1.60, the transparency may decrease or haze may increase due to scattering. is there.

The surface-treated high refractive index fine particles (B) preferably have a surface charge amount (Q _B ) in the range of 25 to 100 μeq / g, more preferably 30 to 100 μeq / g. When the surface charge amount (Q _B ) is small, the hydrophobicity is too high, so that it may not be unevenly distributed in the lower part of the transparent film, and regular irregularities may not be formed on the surface of the transparent film. If the surface charge (Q _B ) is too high,
Affinities with the resin that is the matrix-forming component may be low and may aggregate, and the high-refractive-index fine particles (B) that are surface-treated when the film is formed are not unevenly distributed in the lower layer. Unevenness may not be formed.

Surface charge amount (Q _A ) of surface treated low refractive index fine particles ( _A ) and surface treated high refractive index fine particles (B)
The difference (Q _B ) − (Q _A ) from the surface charge amount (Q _B ) is 20 to 95 μeq / g, more preferably 25 to
It is preferably in the range of 85 μeq / g. If the difference in charge amount is small, it differs depending on the resin that is the matrix forming component, but the difference in surface charge amount between the surface-treated low refractive index fine particles (A) and the surface treated high refractive index fine particles (B) is small, that is, The difference in affinity with the matrix-forming component is low, the separation of these fine particles is insufficient, and the antireflection performance and stringproof performance of the resulting transparent coating may be insufficient. When the charge difference is large, the surface-treated low refractive index fine particles (A)
And the surface-treated high refractive index fine particles (B) may also aggregate, resulting in whitening of the resulting film and insufficient adhesion and strength to the substrate.

The method for measuring the surface charge amount of the surface-treated low refractive index fine particles (B) is the same as that for the surface-treated low refractive index fine particles (A).
The concentration of the surface-treated high refractive index fine particles (B) in the paint for forming a transparent film is 0.1
It is preferably in the range of ˜10% by weight, more preferably 0.2 to 5% by weight. When the concentration of the high refractive index fine particles (B) is low, the effect of improving the antireflection performance is insufficient because a fine refractive index layer cannot be formed in the lower layer of the transparent film, and the effect of improving the bright spot contrast is insufficient. May be. When the concentration of the high refractive index fine particles (B) is high, the fine particle layer with a high refractive index is laminated non-uniformly on the lower layer of the transparent coating, resulting in uneven thickness of the transparent coating or regular irregularities on the surface of the transparent coating. For this reason, the string-proof performance may not be sufficiently exhibited, and the scratch resistance of the transparent film may be insufficient.

Matrix-forming component As the matrix-forming component, a silicone-based matrix-forming component, an organic resin-based matrix-forming component, or the like is used.

As the silicone-based matrix-forming component, an organosilicon compound represented by the following formula (5) and / or a hydrolyzate or hydrolyzed polycondensate thereof is preferably used.
_{R n -SiX 4-n (5} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
Examples of the organosilicon compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane. , Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3- Trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxy Silane, γ-glycidoxymethyltriexisilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acrylooxypropyltrimethoxy Silane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) a Acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysiloctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, , Isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyl Triisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N- β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane and the like can be mentioned.

Examples of the organic resin matrix forming component include known thermosetting resins, thermoplastic resins, electron beam curable resins, and the like as coating resins.
Examples of such resins include conventionally used thermoplastic resins such as polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, and silicone rubbers. , Urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester resin, thermosetting acrylic resin, UV curable acrylic resin, etc., UV curable type An acrylic resin etc. are mentioned. Further, it may be a copolymer or modified body of two or more of these resins.

  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.

The matrix-forming component used in the present invention is preferably composed of a hydrophilic matrix-forming component and a hydrophobic matrix-forming component.
As the hydrophilic silicone (sol-gel) matrix forming component, an organosilicon compound represented by the following formula (1) or a hydrolyzate or hydrolyzed polycondensate thereof is used.
SiX ₄ (1)
(Where X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen)
Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, hydrolyzate thereof, hydrolyzed polycondensate, and the like can be preferably used.

As the hydrophobic silicone-based (sol-gel-based) matrix-forming component, an organosilicon compound represented by the following formula (2), a hydrolyzate thereof, or a hydrolyzed polycondensate is used.
R _n -SiX _4-n (2)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 1 to 3)
Of these, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, and their hydrolysates and hydrolyzed polycondensates can be preferably used.

Examples of the hydrophilic organic resin matrix forming component include polyfunctional (meth) acrylic acid ester resins having a hydrophilic functional group such as a hydroxyl group (OH group), an amino group, a carboxyl group, and a sulfo group. In particular, pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra () having a hydrophilic functional group such as a hydroxyl group (OH group), amino group, carboxyl group, and sulfo group ( In addition to (meth) acrylate, dipentaerythritol hexaacrylate, etc., diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, methoxytriethylene glycol dimethacrylate Butoxy diethylene glycol methacrylate and mixtures thereof.
Examples of the hydrophobic organic resin matrix forming component include polyfunctional (meth) acrylic ester resins having hydrophobic functional groups such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF ₂ group and the like. Specifically, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexane Sanji ol dimethacrylate, perfluorooctyl methacrylate, trifluoroethyl Mete chestnut rate, urethane acrylate and the like and mixtures thereof.
When the hydrophilic matrix-forming component is mixed with a hydrophobic matrix-forming component, the surface-treated low refractive index fine particles (A) are easily separated into the upper layer, and the surface-treated high refractive index fine particles (B) are easily separated into the lower layer. It becomes easy to obtain a membrane separated into two layers.
The concentration ratio (C _MA ) / (C _MB ) of the concentration (C _MA ) as the solid content of the hydrophilic matrix forming component and the concentration (C _MB ) as the solid content of the hydrophobic matrix forming component is 0.01 to 1 , 0, and preferably in the range of 0.05 to 0.5.
When the concentration ratio (C _MA ) / (C _MB ) is less than 0.1, the hydrophilic matrix-forming component is small, and it is close to only the hydrophobic matrix-forming component, and the surface-treated low refractive index fine particles (A ) And the surface-treated high-refractive-index fine particles (B) are insufficiently separated in the vertical direction.
When the concentration ratio (C _MA ) / (C _MB ) exceeds 1, surface-treated high refractive index fine particles having a large amount of hydrophilic matrix-forming components and a high surface charge amount are not unevenly distributed only in the lower layer. There is a case.

The concentration of the matrix-forming component in the coating for forming a transparent film is preferably in the range of 1 to 30% by weight, more preferably 2 to 20% by weight as the solid content.
When the concentration of the matrix-forming component is less than 1% by weight as the solid content, there are cases where there are too many fine particles relative to the matrix, and the film thickness of the transparent coating obtained by non-uniform lamination of the particles becomes non-uniform, Regular irregularities cannot be formed on the surface of the transparent coating, which may result in inadequate string-proof performance and insufficient scratch resistance of the transparent coating.

  When the concentration of the matrix-forming component exceeds 30% by weight as the solid content, there are cases where the amount of fine particles is too small with respect to the matrix, resulting in insufficient antireflection performance and stringproof performance, and insufficient effect of improving bright place contrast. It may become.

Solvent As the solvent used in the present invention, it is possible to dissolve or disperse the matrix forming component and the polymerization initiator and to uniformly disperse the surface-treated low refractive index particles (A) and the surface-treated high refractive index fine particles (B). There is no restriction | limiting in particular and a conventionally well-known solvent can be used.

  Specifically, alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone Ketones such as acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like.

Among these, a solvent having a carbonyl group can be preferably used.
When a solvent having a carbonyl group is contained, the surface-treated low refractive index fine particles (A) and the surface treated high refractive index fine particles (B) are uniformly dispersed, and the paint has good stability, uniformity, In addition to excellent adhesion to the material, strength, etc., it is possible to form a transparent film having irregularities with good reproducibility.

These may be used singly or in combination of two or more. In the present invention, it is preferable to use a mixture of two or more solvents having different boiling points.
In the present invention, the solvent is a mixed solvent of the solvent (A) having a boiling point of 50 to 100 ° C. and the solvent (B) having a boiling point of more than 100 to 200 ° C., and the ratio of the solvent (A) in the mixed solvent is It is preferably in the range of 50 to 90% by weight, and the ratio of the solvent (B) is preferably in the range of 10 to 50% by weight.

As the solvent (A), methanol, ethanol, propanol, 2-propanol (IPA
Alcohols such as acetic acid methyl ester, ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; and toluene. These may be used singly or in combination of two or more.

As the solvent (B), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, alcohols such as ethylene glycol, hexylene glycol, isopropyl glycol; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethers such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether; ketones such as methyl isobutyl ketone, acetylacetone, acetoacetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone Etc. These may be used singly or in combination of two or more.

When the ratio of the solvent (A) in the mixed solvent exceeds 90% by weight, the coating film is dried too fast and the transparent coating film may not become dense, and the hardness and scratch resistance may be insufficient.
When the ratio of the solvent (A) in the mixed solvent is less than 50% by weight, on the other hand, the solvent (B) exceeds 50% by weight, the drying of the coating film becomes slow, and the flattening of the coating film surface proceeds. Therefore, the difference between the height of the convex portion of the transparent coating (T _convex ) and the height of the concave portion (T _concave ) (T _convex )-(T _concave ) may be less than 30 nm. It may not be obtained.
A more desirable ratio of the solvent (B) in the mixed solvent is in the range of 20 to 40% by weight.

The ratio of the solvent in the coating material for forming a transparent film is preferably in the range of about 50 to 99% by weight, more preferably 70 to 98% by weight.
Polymerization initiator The transparent film-forming paint of the present invention contains a polymerization initiator.
The polymerization initiator is not particularly limited as long as the matrix-forming component can be polymerized and cured, and can be appropriately selected depending on the resin, and conventionally known polymerization initiators can be used.

  For example, in addition to polymerization initiators such as acylphosphine oxides, acetophenones, propiophenones, benzyls, benzoins, benzophenones, and thioxanthones, cationic photopolymerization initiators and the like can be mentioned.

The concentration of the polymerization initiator in the coating for forming a transparent film varies depending on the type of the matrix-forming component, but when the matrix-forming component and the polymerization initiator are solids, 0.1 to 20% by weight of the matrix-forming component, Is preferably in the range of 0.5 to 10% by weight.

When the content of the polymerization initiator is less than 0.1% by weight of the matrix-forming component as a solid content, the coating film may be insufficiently cured.
When the content of the polymerization initiator exceeds 20% by weight of the matrix-forming component as a solid content, the stability of the paint may be insufficient, or the hardness of the resulting transparent film may be insufficient.

A conventionally well-known method can be employ | adopted as a method of forming a transparent film using the coating material for transparent film formation which concerns on this invention.
Specifically, the transparent film-forming paint is applied to the substrate by a known method such as dipping, spraying, spinner, roll coating, bar coating, slit coater printing, gravure printing, or micro gravure printing. A transparent film can be formed by applying, drying, and curing by conventional methods such as ultraviolet irradiation, heat treatment, etc.In the present invention, roll coating, slit coater printing, gravure printing, and micro gravure printing are used. Recommended.
The substrate with a transparent coating The substrate with a transparent coating according to the present invention is a substrate with a transparent coating in which a transparent coating having irregularities on the surface is formed on the substrate, and the low refractive index obtained by surface treatment of the transparent coating. It consists of fine particles (A), surface-treated high refractive index fine particles (B), and matrix components, and the surface-treated low refractive index fine particles (A) are unevenly distributed in a layer on the top of the transparent coating, and surface-treated high refractive index Fine particles (B) are unevenly distributed in the lower part of the transparent film, the average film thickness of the transparent film is in the range of 1 to 10 μm, and the height of the convex part of the transparent film (T _convex ) and the height of the _{concave part} (T _concave ) (T _convex ) − (T _concave ) is in the range of 30 to 1500 nm.
The substrate with a transparent coating according to the present invention is preferably a substrate having a transparent coating formed on the substrate using the coating material for forming a transparent coating.
Example of substrate with transparent coating FIGS. 1, 2 and 3 schematically show examples of the substrate with a transparent coating of the present invention.

The upper white circle is a low refractive index fine particle, the lower black circle is a high refractive index fine particle, the other white spot is a matrix component, and there are irregularities on the upper part of the transparent film.
Base materials: Base materials include cellulose base materials such as triacetyl cellulose film, diacetyl cellulose film and acetate butyrate cellulose film, polyester base materials such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, and cyclic polyolefin film. In addition to polyolefin base materials such as nylon-6, nylon-66, etc., polyacrylic films, polyurethane films, polycarbonate films, polyether films, polyethersulfone films, polystyrene films, etc. Examples of the base material include polymethylpentene film, polyetherketone film, and acrylonitrile film. In addition, a coated substrate in which another coating such as a hard coat film is formed on such a substrate can also be used.

Transparent coating The transparent coating comprises a surface-treated low refractive index fine particle (A), a surface-treated high refractive index fine particle (B), and a matrix component. As the surface-treated low refractive index fine particles (A), the same particles as described above can be used.

The content of the surface-treated low refractive index fine particles (A) in the transparent coating is 1 to 30% by weight as a solid content
Further, it is preferably in the range of 2 to 25% by weight. If the content of the low refractive index fine particles (A) is small, the refractive index of the upper part of the transparent film will not be sufficiently low, so the reflectivity of the transparent film will be high and the antireflection performance will be insufficient, or the contrast in the light place will be insufficient. It may become. If the content of the low refractive index fine particles (A) is large, the amount of the low refractive index fine particles (A) is too much to separate from the surface-treated low refractive index fine particles (B), resulting in unevenness in the range described later. Formation of a transparent coating becomes difficult and the string-proof performance may be insufficient.

As the surface-treated low refractive index fine particles (B), the same particles as described above can be used. The content of the surface-treated high refractive index fine particles (B) in the transparent coating is 5 to 70% by weight as a solid content
Further, it is preferably in the range of 10 to 50% by weight. If the content of the high refractive index fine particles (B) is small, irregularities on the surface of the transparent coating may be insufficient and the string-proof performance may be insufficient. If the content of the high refractive index fine particles (B) is large, the film thickness of the transparent film may become nonuniform or the scratch resistance may be insufficient.

Matrix Component As the matrix component, a silicone (sol-gel) matrix component, an organic resin matrix component, or the like is used. As the silicone matrix component, the above formula (5)
The same hydrolyzed polycondensates of organosilicon compounds are preferably used. Examples of the organic resin-based matrix component include known thermosetting resins, thermoplastic resins, and electron beam curable resins as coating resins.

  Examples of such resins include conventionally used thermoplastic resins such as polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, and silicone rubbers. , Urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester resin, thermosetting acrylic resin, UV curable acrylic resin, etc., UV curable type An acrylic resin etc. are mentioned. Further, it may be a copolymer or modified body of two or more of these resins.

  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.

The matrix component used in the present invention is preferably composed of a hydrophilic matrix component and a hydrophobic matrix component.
As the hydrophilic silicone (sol-gel) matrix component, a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (3) is used.
SiX ₄ (3)
(Where X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen)
Specifically, hydrolyzed polycondensates of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and methyltrimethoxysilane can be suitably used.
As the hydrophobic silicone (sol-gel) matrix component, a hydrolyzed polycondensate of an organosilicon compound represented by the following formula (4) is used.
_{R n -SiX 4-n (4} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 1 to 3)
Among these, hydrolysis polycondensates of 3,3,3-trifluoropropyltrimethoxysilane and methyl-3,3,3-trifluoropropyldimethoxysilane can be preferably used.

Examples of hydrophilic organic resin matrix components include polyfunctional (meth) acrylic acid ester resins having hydrophilic functional groups such as hydroxyl groups (OH groups), amino groups, carboxyl groups, and sulfo groups. Include pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meta) having hydrophilic functional groups such as hydroxyl group (OH group), amino group, carboxyl group, and sulfo group. ) In addition to acrylate, dipentaerythritol hexaacrylate, etc., diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, methoxytriethylene glycol dimethacrylate, Alkoxy diethyleneglycol methacrylate and mixtures thereof.

Examples of the hydrophobic organic resin matrix component include polyfunctional (meth) acrylic acid ester resins having a hydrophobic functional group such as vinyl group, urethane group, epoxy group, (meth) acryloyl group, CF ₂ group, Specifically, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl Methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexa Diol dimethacrylate, perfluorooctyl methacrylate, trifluoroethyl Mete chestnut rate, urethane acrylate and the like and mixtures thereof.

The content of the solid content of the hydrophilic matrix components (W _MA) and the content of the solid content of the hydrophobic matrix components (W _MB) and the ratio of the content of _{(W MA) / (W MB} ) 0.01 It is preferable to be in the range of ˜1, more preferably 0.05 to 0.5.

When (W _MA ) / (W _MB ) is small, there are few hydrophilic matrix-forming components and it is close to only hydrophobic matrix-forming components, and surface-treated low refractive index fine particles (A) (top) and surface treatment In some cases, a transparent coating separated into the high refractive index fine particles (B) (lower part) cannot be obtained. When (W _MA ) / (W _MB ) is large, the surface-treated high refractive index fine particles (B) having a large amount of hydrophilic matrix components and a high surface charge amount may not be unevenly distributed only in the lower layer. .

The content (W _MA ) of the matrix component in the transparent film is preferably in the range of 25 to 94% by weight, more preferably 30 to 90% by weight.
If the content of the matrix component (W _MA ) in the transparent film is small, the ratio of the particles in the film is too high, and the surface-treated low refractive index fine particles (A) and the surface treated high refractive index fine particles (B) Since a separated transparent film cannot be obtained, the antireflection performance and stringproof performance may be insufficient, and the strength and scratch resistance of the transparent film may be insufficient. When the content of the matrix component (W _MA ) in the transparent coating is large, the amount of particles is small, so that the effects of the present invention, that is, the antireflection performance, the stringproof performance, and in some cases, the antistatic performance are insufficient. There is a case.

As for the film thickness of the transparent film according to the present invention, the average film thickness of the transparent film is preferably in the range of 1 to 10 μm, more preferably 2 to 8 μm. Here, the average film thickness refers to the average value of the average height of convex portions (T _convex ) and the average height of concave portions (T _concave ) of the transparent coating.

  When the average film thickness of the transparent film is less than 1 μm, it is difficult to form a transparent film having two layers and having irregularities described later. When the average film thickness of the transparent film exceeds 10 μm, the transparent film is cracked. When the substrate is made of plastic or the like, curling (curving or warping) may occur.

Further, the difference (T _convex ) − (T _concave ) between the average height of convex portions (T _convex ) and the average height of concave portions (T _concave ) of the transparent coating is in the range of 30 to 1500 nm, and further 50 to 1000 nm. Preferably there is.

If (T- _convex )-(T- _concave ) is small, sufficient string resistance may not be obtained. Even if (T- _convex )-(T- _concave ) is too large, the surface scattering of light may appear large and whitish.
Furthermore, the thickness of the surface-treated low refractive index fine particles (A) unevenly distributed on the transparent film is preferably in the range of about 10 to 500 nm, more preferably 20 to 300 nm, and particularly preferably 50 to 200 nm.

When the thickness of the layer of the low refractive index fine particles (A) is small, the antireflection performance may be insufficient. If the layer of the low refractive index fine particles (A) is too thick, the thickness may deviate from the Fresnel principle, resulting in inadequate antireflection performance or reduced bright room contrast. May be white.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[Example 1]
Preparation of paint for forming transparent film (A-1) Silica hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium as low refractive index component : Isopropanol (particle refractive index: 1.30). 100 g of this sol was mixed with 10 g of perfluorooctylethyltriethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-158E, SiO ₂ component 26.6 wt%), 10 g of ultrapure water was added, and the mixture was stirred at 40 ° C. for 5 hours. Thus, a silica-based hollow fine particle-dispersed sol which was surface-treated was obtained (solid content 19.3%). The surface charge amount of this surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 8.3 μeq / g. Titanium oxide particles (manufactured by Catalyst Chemical Industry Co., Ltd .: titanium microbeads, average particle diameter of 3 μm, particle refractive index of 2.40) were used as the high refractive index component. 20.5 g of this titanium oxide particle is put in 79.5 g of ethyl alcohol, and 2.52 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103, SiO ₂ component 81.2%). ), 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated titanium oxide particle dispersion (solid content: 20.0%). The surface charge amount of this surface-treated titanium oxide particle dispersion was measured and found to be 30.0 μeq / g. Surface-treated silica-based hollow fine particle dispersion 7.7 g, surface-treated titanium oxide particle dispersion 30 g, 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix and a hydrophilic matrix As 2.7 g of 2-hydroxy-3acryloyloxypropyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester G-201P), dissolved in photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., IPA), solid 10%) (partial concentration: 10%) and 13.2 g of isopropanol, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether as a solvent were mixed thoroughly to form a coating material for forming a transparent film (A-1). Prepared.

Preparation of transparent film-coated substrate (1) Transparent film-forming coating solution (A-1) was coated with a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, haze 1.0%, reflection) After coating with a bar coater at a rate of 5.1% and drying at 70 ° C. for 1 minute, the substrate was coated with a transparent film by irradiating with a high-pressure mercury lamp (80 W / cm) for 1 minute to cure (1) Was prepared. A part of the transparent coating was cut perpendicularly in the vertical direction, and the cross section was observed with a transmission electron microscope. Silica hollow fine particles formed a layer with a thickness of about 100 nm on the top, and the presence of titanium oxide particles on the bottom. Was recognized. The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate (1) with a transparent coating were measured, and the results are shown in the table.

The total light transmittance and haze were measured with a haze meter (Nippon Denshoku Co., Ltd .: NDH2000), and the reflectance was measured with a spectrophotometer (Nippon Bunko Co., Ltd .: Ubest-55).
Moreover, anti-glare property, adhesiveness, and pencil hardness were evaluated by the following methods and evaluation criteria, and the results are shown in the table.
Anti-glare base material with anti-glare coating with hard coat function (1) The anti-glare property of the base material is uniformly applied with black spray on the back side of the base material. Antiglare property was evaluated. The results are shown in the table.

I can't see any fluorescent lights: ◎
Fluorescent light is slightly visible: ○
Fluorescent lamp is visible but outline is blurred: △
Fluorescent light is clearly visible: ×
Adhesion 1 on the surface of the base material with anti-reflective coating with hard coat function (1) with 1mm vertical and horizontal intervals with a knife
One parallel scratch was made to make 100 squares, cellophane tape was adhered to this, and when the cellophane tape was peeled off, the number of squares remaining after the coating was not peeled The adhesion was evaluated by classifying into 4 stages. The results are shown in the table.

Number of remaining squares: ◎
Number of remaining squares 90-99: ○
Number of remaining squares: 85 to 89: Δ
Number of remaining squares: 84 or less: ×
Pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.

A part of the film of the substrate with transparent film (1) is peeled off, and the difference between the average film thickness of the transparent film and the height of the convex part (T ₁ ) and the height of the concave part (T ₂ ) is measured with a laser microscope (KEYENCE CORPORATION Measured using VE-3000) and shown in the table.

[Example 2]
Preparation of paint for forming transparent film (A-2) In Example 1, the same procedure was followed except that 7.7 g of the surface-treated silica-based hollow fine particle dispersion and 45 g of the surface-treated titanium oxide particle dispersion were used. A forming paint (A-2) was prepared.

Preparation of substrate with transparent film (2) A substrate with transparent film (2) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (A-2) was used. When the cross section of the transparent film was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 100 nm on the upper part, and the presence of titanium oxide particles was observed on the lower part.

The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate (2) with a transparent coating were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Example 3]
Preparation of paint for forming transparent film (A-3) Transparent film was prepared in the same manner as in Example 1, except that 7.7 g of the surface-treated silica-based hollow fine particle dispersion and 10 g of the surface-treated titanium oxide particle dispersion were used. A forming paint (A-3) was prepared.

Preparation of substrate with transparent film (3) A substrate with transparent film (3) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (A-3) was used. When the cross section of the transparent film was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 100 nm on the upper part, and the presence of titanium oxide particles was observed on the lower part.
The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate (3) with a transparent coating were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Example 4]
Preparation of Transparent Film Forming Coating Material (A-4) In Example 1, titanium oxide particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: titanium microbead, average particle diameter 4.5 μm, particle refractive index 2. A transparent film-forming paint (A-4) was prepared in the same manner except that 40) was used.

Preparation of substrate with transparent film (4) A substrate with transparent film (4) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (A-4) was used. When the cross section of the transparent film was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 100 nm on the upper part, and the presence of titanium oxide particles was observed on the lower part.

The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate (4) with a transparent coating were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Example 5]
Preparation of paint for forming transparent film (A-5) In Example 1, titanium oxide particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: titanium microbead, average particle diameter 1 μm, particle refractive index 2.40) as a high refractive index component A transparent film-forming paint (A-5) was prepared in the same manner except that was used.

Preparation of substrate with transparent coating (5)
A substrate with a transparent film (5) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-5) was used. When the cross section of the transparent film was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 100 nm on the upper part, and the presence of titanium oxide particles was observed on the lower part.

The total light transmittance, haze, and reflectance of light with a wavelength of 550 nm of the obtained substrate (5) with a transparent coating were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Example 6]
Preparation of paint for forming transparent film (A-6) In Example 1, the same procedure was followed except that 15.5 g of the surface-treated silica-based hollow fine particle dispersion and 30 g of the surface-treated titanium oxide particle dispersion were used. A forming paint (A-6) was prepared.

Preparation of substrate with transparent film (6) A substrate with transparent film (6) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (A-6) was used. When the cross section of the transparent coating was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 200 nm on the top, and the presence of titanium oxide particles was observed on the bottom. The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate (6) with a transparent coating were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .

[Example 7]
Preparation of Transparent Film Forming Coating Material (A-7) In Example 1, except for using 5 g of surface-treated silica-based hollow fine particle dispersion and 30 g of surface-treated titanium oxide particle dispersion, A paint (A-7) was prepared.

Preparation of substrate with transparent film (7) A substrate with transparent film (7) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (A-7) was used. When the cross section of the transparent coating was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 70 nm on the top, and the presence of titanium oxide particles was observed on the bottom.
The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained transparent film-coated substrate (7) were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Example 8]
Preparation of paint for forming transparent film (A-8) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5% by weight, dispersion medium as low refractive index component : Isopropanol (particle refractive index: 1.30). To 100 g of this sol, 5.12 g of tridecyl methacrylate (Light Ester TD manufactured by Kyoeisha Chemical Co., Ltd.) was mixed and stirred at 50 ° C. for 24 hours to obtain a silica-based hollow fine particle dispersed sol (solid content: 24.4%). The surface charge amount of the surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 6.0 μeq / g.

Titanium oxide particles (manufactured by Catalyst Chemical Industry Co., Ltd .: titanium microbeads, average particle diameter of 3 μm, particle refractive index of 2.40) were used as the high refractive index component. 20.5 g of this titanium oxide particle is put in 79.5 g of ethyl alcohol, and 2.52 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, SiO ₂ component 81.9% by weight). ), 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated titanium oxide particle dispersion (solid content: 20.0 wt%). The surface charge amount of this surface-treated titanium oxide particle dispersion was measured and found to be 39.2 μeq / g. Surface-treated silica-based hollow fine particle dispersion 7.7 g, surface-treated titanium oxide particle dispersion 30 g, 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix and a hydrophilic matrix As 2.7 g of 2-hydroxy-3acryloyloxypropyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester G-201P), dissolved in photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., IPA), solid 0.35 g (concentration concentration 10% by weight) and 20.95 g of isopropanol, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether as a solvent were mixed thoroughly to form a coating material for forming a transparent film (A-8) Was prepared.

Preparation of substrate with transparent film (8) A substrate with transparent film (8) was prepared in the same manner as in Example 1, except that the coating liquid for forming a transparent film (A-8) was used. When the cross section of the transparent film was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 100 nm on the upper part, and the presence of titanium oxide particles was observed on the lower part.

The total light transmittance, haze, and reflectance of light with a wavelength of 550 nm of the obtained substrate (8) with a transparent coating were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Example 9]
Preparation of paint for forming transparent film (A-9) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 120 nm, concentration 20.5 wt%, dispersion medium as low refractive index component : Isopropanol (particle refractive index: 1.20). Silica-based hollow fine particle dispersion sol in which 10 g of perfluorooctylethyltriethoxysilane (AY43-158E 100% manufactured by Toray Dow Corning) was mixed with 100 g of this sol, 10 g of ultrapure water was added, and the surface treatment was performed by stirring at 40 ° C. for 5 hours. (Solid content 19.3%) was obtained. The surface charge amount of the surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 7.7 μeq / g. Titanium oxide particles (manufactured by Catalyst Chemical Industry Co., Ltd .: titanium microbeads, average particle diameter of 3 μm, particle refractive index of 2.40) were used as the high refractive index component. 20.5 g of this titanium oxide particle is put in 79.5 g of ethyl alcohol, and 2.52 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103 SiO 2 component 81.2%) is added. After mixing, 10 g of ultrapure water was added and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated titanium oxide particle dispersion (solid content: 20.0 wt%). The surface charge amount of this surface-treated titanium oxide particle dispersion was measured and found to be 30.0 μeq / g. Surface-treated silica-based hollow fine particle dispersion 7.7 g, surface-treated titanium oxide particle dispersion 30 g, 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix and a hydrophilic matrix As 2.7 g of 2-hydroxy-3acryloyloxypropyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester G-201P), dissolved in photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., IPA), solid 0.35 g (concentration of 10% by weight) and 20.95 g of isopropanol, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether as a solvent were mixed thoroughly to form a transparent film-forming paint (A-9) Was prepared.

Preparation of substrate with transparent film (9) A substrate with transparent film (9) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-9) was used. When the cross section of the transparent film was observed with a transmission electron microscope, silica-based hollow fine particles formed a layer having a thickness of about 130 nm on the upper part, and presence of titanium oxide particles was observed on the lower part.

The total light transmittance, haze, and reflectance of light with a wavelength of 550 nm of the obtained substrate (9) with a transparent coating were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Example 10]
Preparation of coating film for forming transparent film (A-10) Silica hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium as low refractive index component : Isopropanol (particle refractive index: 1.30). Silica-based hollow fine particle dispersion sol in which 10 g of perfluorooctylethyltriethoxysilane (AY43-158E 100% manufactured by Toray Dow Corning) was mixed with 100 g of this sol, 10 g of ultrapure water was added, and the surface treatment was performed by stirring at 40 ° C. for 5 hours. (Solid content 19.3%) was obtained. The surface charge amount of this surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 8.3 μeq / g. Silica zirconia particles (manufactured by Catalyst Chemical Industry Co., Ltd .: silica microbead P-500K1.52C, average particle diameter 3 μm, particle refractive index 1.52) were used as the high refractive index component. 20.5 g of the silica zirconia particles are put in 79.5 g of ethyl alcohol, and 2.52 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd .: KBM-5103, SiO ₂ component 81. 2 wt%), 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated silica zirconia particle dispersion (solid content: 20.0%). The surface charge amount of the surface-treated silica zirconia particle dispersion was measured and found to be 41.3 μeq / g. Surface-treated silica-based hollow fine particle dispersion 15.5 g, surface-treated silica zirconia particle dispersion 30 g, 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix and hydrophilic matrix As 2.7 g of 2-hydroxy-3acryloyloxypropyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light ester G-201P), dissolved in photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., IPA), solid (10% by weight concentration) 0.35 g and 20-95 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether Was prepared.

Preparation of substrate with transparent coating (10) A substrate with transparent coating (10) was prepared in the same manner as in Example 1, except that the coating solution for forming a transparent coating (A-10) was used. When the cross section of the transparent film was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 100 nm on the top, and the presence of silica zirconia particles was observed on the bottom.

The total light transmittance, haze, and reflectance of light with a wavelength of 550 nm of the obtained substrate (10) with a transparent coating were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Example 11]
Preparation of substrate (11) with transparent coating A transparent coating-forming coating material (A-1) prepared in the same manner as in Example 1 was applied to a TAC film (thickness 80
μm, refractive index 1.48, substrate transmittance 88.0%, Haze 0.1%, reflectivity 4.8%) with a bar coater, dried at 70 ° C. for 1 minute, and then high pressure A substrate with a transparent coating (11) was prepared by curing by irradiation with a mercury lamp (80 W / cm) for 1 minute. When the cross section of the transparent film was observed with a transmission electron microscope, the silica-based hollow fine particles formed a layer having a thickness of about 100 nm on the upper part, and the presence of titanium oxide particles was observed on the lower part.

The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate with transparent coating (11) were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Comparative Example 1]
Preparation of coating solution (AR1) for forming an antireflection layer As a low refractive index component, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, concentration 20.5 wt%, dispersion medium : Isopropanol (particle refractive index: 1.30). Silica-based hollow surface-treated by mixing 10 g of perfluorooctylethyltriethoxysilane (manufactured by Toray Dow Corning: AY43-158E, 100 wt%) with 100 g of this sol, adding 10 g of ultrapure water, and stirring at 40 ° C. for 5 hours. A fine particle dispersed sol was obtained (solid content 19.3% by weight). The surface charge amount of this surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 8.3 μeq / g.

The surface-treated silica-based hollow fine particle dispersion 7.7 g and the hydrophobic matrix hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 24.3 g
0.35 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10% by weight) and 419 g of isopropanol, 160 g of methyl isobutyl ketone, and 120 g of propylene glycol monomethyl ether as a solvent By mixing, an antireflection layer-forming coating solution (RR1) was prepared.
Preparation of coating solution (AG1) for forming a high refractive index layer Titanium oxide particles (manufactured by Catalyst Chemical Industry Co., Ltd .: titanium microbead, average particle diameter of 3 μm, particle refractive index of 2.40) were used as a high refractive index component. 20.5 g of this titanium oxide particle was put into 79.5 g of ethyl alcohol, and 2.52 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd .: KBM-5103, SiO ₂ component 81. 2 wt%) was added, 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated titanium oxide particle dispersion (solid content: 20.0 wt%). The surface charge amount of this surface-treated titanium oxide particle dispersion was measured and found to be 30.0 μeq / g. 30 g of the surface-treated titanium oxide particle dispersion, 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as the hydrophobic matrix and 2-hydroxy-3acryloyloxypropyl methacrylate (as the hydrophilic matrix) 2.7 g of Kyoeisha Chemical Co., Ltd .: Light Ester G-201P) 0.35 g of photoinitiator (Irgacure 184, Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10 wt%) and isopropano as solvent -A coating solution (AG1) for forming a high refractive index layer was prepared by sufficiently mixing 13.2 g of methyl, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether.

Preparation of substrate with transparent film (R1) A coating solution (AG1) for forming a high refractive index layer was prepared from a PET film (thickness 100 μm, refractive index 1.65,
The substrate transmittance was 88.0%, the haze was 1.0%, and the reflectance was 5.1%. After coating with a bar coater and drying at 70 ° C. for 1 minute, a high pressure mercury lamp (80 W / cm) was applied. The high refractive index layer was formed by irradiating for a minute and curing. The average film thickness of the high refractive index layer was 4.5 μm, and the difference between the height of the protrusion (T ₁ ) and the height of the recess (T ₂ ) was 20 nm.
Next, a coating solution (RR1) for forming an antireflection layer was applied onto the high refractive index layer with a bar coater, and the temperature was 70 ° C.
After drying for 1 minute, a high pressure mercury lamp (80 W / cm) was irradiated for 1 minute to cure and form an antireflection layer to prepare a transparent coated substrate (R1).

The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained transparent film-coated substrate (R1) were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Comparative Example 2]
Preparation of Transparent Film Forming Paint (R2) As a low refractive index component, silica-based hollow fine particle dispersed sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria 1420, average particle diameter 60 nm, concentration 20.5% by weight, dispersion medium: isopropano The particle refractive index 1.30) was used. Silica-based hollow fine particles prepared by mixing 5 g of vinyl silane (KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd., 62.7% by weight of SiO ₂ component) with 10 g of this sol, adding 10 g of ultrapure water, stirring the mixture at 40 ° C. for 5 hours, and then surface-treating. A dispersion sol was obtained (solid content 20.6% by weight). The surface charge amount of the surface-treated silica-based hollow fine particle dispersed sol was measured and found to be 3.3 μeq / g. Titanium oxide particles (manufactured by Catalyst Chemical Industry Co., Ltd .: titanium microbeads, average particle diameter of 3 μm, particle refractive index of 2.40) were used as the high refractive index component. 20.5 g of this titanium oxide particle is put in 79.5 g of isopropanol, 2.52 g of vinylsilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-1003 SiO2 component 62.7%) is mixed, and 10 g of ultrapure water is mixed. The titanium oxide particle dispersion was added and stirred for 5 hours at 40 ° C. to obtain a surface-treated titanium oxide particle dispersion (solid content: 20.0%). The surface charge amount of the surface-treated titanium oxide particle dispersion was measured and found to be 4.0 μeq / g. Surface treated silica-based hollow fine particle dispersion sol 10.54 g, surface treated titanium oxide particle dispersion 30 g, pentaerythritol triacetate (Kyoeisha Chemical Co., Ltd .: PE-3A) 24 g, and diethylaminoethyl methacrylate (Kyoeisha Chemical Co., Ltd.): 3 g of light ester DE) 0.42 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10%) and 1/1 (weight ratio) mixing of isopropanol and methyl isobutyl ketone A transparent film-forming paint (R2) was prepared by thoroughly mixing 62.04 g of the solvent.
Preparation of substrate (R2) with a transparent coating A coating (R2) for forming a transparent coating was formed by using a PET film (thickness 100 μm, refractive index 1.65, substrate transmittance 88.0%, Haze 1.0%, reflectance 5.1%). ) Was coated with a bar coater, dried at 70 ° C. for 1 minute, and then irradiated with a high-pressure mercury lamp (80 W / cm) for 1 minute to cure, thereby preparing a substrate (R2) with a transparent coating. When a part of the transparent coating was cut perpendicularly in the longitudinal direction and the cross section was observed with a transmission electron microscope, silica-based hollow fine particles and titanium oxide particles were present in the film in a monodispersed form.
The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate with transparent coating (R2) were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .
[Comparative Example 3]
Preparation of paint for forming transparent film (R3) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 60 nm, surface charge 30 μeq / g, concentration 20.5 as low refractive index component % By weight, dispersion medium: 7.7 g of isopropanol particle refractive index 1.30), titanium oxide particles (manufactured by Catalyst Chemical Industry Co., Ltd .: titanium microbead, average particle diameter 3 μm, particle refractive index as a high refractive index component) 2.40, methanol dispersion (solid content concentration 20% by weight) 30 g of surface charge 105 μeq / g), 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix and hydrophilic 2-hydroxy-3acryloyloxypropyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester G-201P) as a functional matrix 7 g, 0.35 g of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10%) and 20.95 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, propylene glycol monomethyl A transparent film-forming paint (R3) was prepared by thoroughly mixing 6.0 g of ether.
Preparation of transparent film-coated substrate (R3) A transparent film-coated substrate (R3) was prepared in the same manner as in Example 1 except that the transparent film-forming coating solution (R3) was used. When the cross section of the transparent film was observed with a transmission electron microscope, the hollow silica fine particles and the titanium oxide particles were present in an aggregated form.

The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained transparent film-coated substrate (R3) were measured, and the results are shown in the table. Moreover, the average film thickness of the transparent film, the difference between the height (T ₁ ) of the convex portion and the height (T ₂ ) of the concave portion, antiglare property, adhesion, and pencil hardness were evaluated, and the results are shown in the table. .

The example of 1 aspect of the base material with a transparent film of this invention is shown typically. The other example of 1 aspect of the base material with a transparent film of this invention is shown typically. The further another example of 1 aspect of the base material with a transparent film of this invention is shown typically.

Claims (11)

A transparent film-forming paint comprising a low-refractive index fine particle and a high-refractive index fine particle having different affinity to the matrix-forming component, a matrix-forming component, a polymerization initiator, and a solvent,
Both low refractive index fine particles and high refractive index fine particles are surface treated with a silane coupling agent, and the refractive index (n _A ) of the surface treated low refractive index fine particles ( _A ) is in the range of 1.20 to 1.45. The average particle diameter is in the range of 5 to 200 nm, the surface charge (Q _A ) is in the range of 5 to 80 μeq / g,
The refractive index (n _B ) of the surface-treated high refractive index fine particles (B) is higher than (n _A ), and the average particle size is 0.5
In the range of -5 μm, the surface charge (Q _B ) is in the range of 25-100 μeq / g, and the concentration of the low refractive index fine particles (A) is in the range of 0.1-10 wt% as the solid content, Transparent, characterized in that the concentration of the high refractive index fine particles (B) is in the range of 0.1 to 10% by weight as the solid content, and the concentration of the matrix forming component as the solid content is in the range of 1 to 30% by weight. Film-forming paint. The difference between the surface charge of the low-refractive index fine particles _(A) (Q A) and the surface charge amount of the high屈率fine particles _{(B) (Q B) (} Q B) - (Q A) is 20～95Myueq / The transparent film-forming paint according to claim 1, which is in the range of g. The matrix-forming component comprises a hydrophilic matrix-forming component and a hydrophobic matrix-forming component, and the concentration of the hydrophilic matrix-forming component as a solid content (C _MA ) and the concentration of the hydrophobic matrix-forming component as a solid content (C _MB The transparent film-forming paint according to claim 1 or 2, wherein the concentration ratio (C _MA ) / (C _MB ) is in the range of 0.01 to 1. The hydrophilic matrix-forming component is an organosilicon compound represented by the following formula (1) or a hydrolyzate thereof, a hydrolyzed polycondensate and / or a polyfunctional (meth) acrylate resin having a hydrophilic functional group And
SiX ₄ (1)
(However, in the formula, X represents an alkoxy group having 1 to 4 carbon atoms, a silanol group, halogen, or hydrogen.)
Polyfunctional (meth) acrylic ester resin in which the hydrophobic matrix forming component has an organosilicon compound represented by the following formula (2) or a hydrolyzate, hydrolyzed polycondensate and / or a hydrophobic functional group thereof The paint for forming a transparent film according to claim 3, wherein _{R n -SiX 4-n (2} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 1 to 3) The hydrophilic functional group is one or more selected from a hydroxyl group, an amino group, a carboxyl group, a sulfo group, and a glycidyl group, and the hydrophobic functional group is a (meth) acryloyl group, an alkyl group,
Phenyl group, a urethane group, transparent film-forming coating material according to claim 3 or 4, wherein the at least one selected from CF ₂ group. The solvent is a mixed solvent of a solvent (A) having a boiling point of 50 to 100 ° C. and a solvent (B) having a boiling point of more than 100 ° C. and to 200 ° C., and the ratio of the solvent (A) in the mixed solvent is The paint for forming a transparent film according to any one of claims 1 to 5, wherein the paint is in the range of 50 to 90% by weight and the ratio of the solvent (B) is in the range of 10 to 50% by weight. A substrate with a transparent coating, on which a transparent coating having irregularities on the surface is formed, a low refractive index fine particle (A) whose surface is treated with a transparent coating and a high refractive index fine particle (B ) And a matrix component, the surface-treated low refractive index fine particles (A) are unevenly distributed in the upper part of the transparent film, and the surface-treated high refractive index fine particles (B) are unevenly distributed in the lower part of the transparent film, The average film thickness of the transparent coating is in the range of 1 to 10 μm,
The difference in the average height of the projections of the transparent film and (T _convex) average height of the recess and (T _concave) (T _convex) - transparent film (T _concave) is characterized in that in the range of 30~1500nm Attached base material. The surface-treated low refractive index fine particles (A) in the transparent film have a refractive index (n _A ) in the range of 1.20 to 1.45, an average particle diameter in the range of 5 to 200 nm, and the surface treated high the refractive index of屈率particles _(B) (n B) is higher than (n _a), the range of average particle diameter of 0.5 to 5 [mu] m, the content of low refractive index particles (a) obtained by surface treatment The solid content is in the range of 1 to 30% by weight, and the content of the surface-treated high refractive index fine particles (B) is in the range of 5 to 70% by weight as the solid content. A substrate with a transparent coating. The matrix component is composed of a hydrophilic matrix component and a hydrophobic matrix component. The content of the hydrophilic matrix component as a solid (W _MA ) and the content of the hydrophobic matrix component as a solid (W _MB ) The substrate with a transparent coating according to claim 7 or 8, wherein the concentration ratio (W _MA ) / (W _MB ) is in the range of 0.01 to 1. The hydrophilic matrix component is a polyfunctional (meth) acrylate resin having a hydrolytic polycondensate of an organosilicon compound represented by the following formula (1) and / or a hydrophilic functional group,
SiX ₄ (3)
(Where X is an alkoxy group having 1 to 4 carbon atoms, silanol group, halogen, hydrogen)
The hydrophobic matrix component is a polyfunctional (meth) acrylic ester resin having a hydrolytic polycondensate of an organosilicon compound represented by the following formula (4) and / or a hydrophobic functional group. The base material with a transparent film in any one of Claims 7-9.
R _n -SiX _4-n (4)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 1 to 3) The hydrophilic functional group is one or more selected from a hydroxyl group, an amino group, a carboxyl group, a sulfo group, and a glycidyl group, and the hydrophobic functional group is a (meth) acryloyl group, an alkyl group,
Phenyl group, a urethane group, with a transparent film substrate according to any one of claims 7 to 10, characterized in that at least one selected from CF ₂ group.

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