JP6910774B2 - An optical film, a base material provided with the optical film, and an optical device having the base material. - Google Patents

Description

The present invention relates to an optical film having excellent transparency, antireflection and antifouling properties, a base material provided with the optical film, and an optical device having the base material.

In the field related to solar panels, there is a demand for a layer having an antireflection function and an antifouling / self-cleaning function on the panel surface. The former function is, for example, a function of preventing a decrease in light transmittance due to visible light reflection on the panel surface and improving power generation efficiency. The latter function is, for example, an antifouling / self-cleaning function against panel stains such as bird droppings, dust, and scale.

Further, in fields related to display devices such as plasma displays (PDPs), electroluminescence displays (ELDs), and liquid crystal displays (LCDs), problems such as contrast deterioration due to reflection of external light, image reflection, and contamination of the display surface are problems. There is. Therefore, there is a demand for an apparatus having excellent antireflection and antifouling properties without deteriorating transparency.

Furthermore, in fields related to optical lenses such as surveillance cameras and telescopes, when images cannot be seen clearly due to image reflection, or when using optical articles such as lenses, stains due to adhesion of hand stains, fingerprints, etc. There is a demand for products that have antifouling properties that can be dealt with.

In response to such demand, inorganic particles such as silica and organic fine particles such as styrene and acrylic are often used as materials for improving antireflection. Specifically, in Patent Document 1, by combining a sol-gel type silicon oxide base material with silicon oxide particles and aluminum oxide, it has good mechanical strength and chemical resistance, and particularly improved reflection. Anti-reflection layers that exhibit anti-reflection properties have been proposed. Further, Patent Document 2 proposes an antireflection layer produced by coating a sol containing tetraalkoxysilane, organosilane, and organofluorosilane, and then gelling the sol.

On the other hand, regarding antifouling property or self-cleaning property, Patent Document 3 proposes to use a fluoropolymer, and Patent Document 4 proposes to use anatase-type titanium oxide particles.

Special Table 2013-537873 Special Table 2014-527098 Japanese Unexamined Patent Publication No. 2002-31205 Japanese Unexamined Patent Publication No. 2013-026243 Japanese Unexamined Patent Publication No. 2001-233611 Japanese Unexamined Patent Publication No. 2008-139581

However, a technique that achieves both antireflection and antifouling properties has not been reported so far.

Further, although it is usually necessary to provide the antifouling layer on the outermost surface, if titanium oxide particles of the submicron order (about 500 nm) as used in Patent Document 4 are used in order to exhibit antifouling property. , There was a problem that transparency was reduced.

Therefore, an object of the present invention is to provide an optical film having excellent transparency and having both antireflection and antifouling properties.

A first aspect of the present invention is (A) a low refractive index material exhibiting a refractive index of 1.22 to 1.32, and (B) a metal containing at least one or more alkoxysilanes and one or more alkoxytitaniums. An optical film containing a composite polymetalloxane containing a condensed structure of an alkoxy, wherein the alkoxysilane of the composite polymetalloxane is at least a cationically polymerizable organic group and a saturated or unsaturated hydrocarbon having 1 to 21 carbon atoms. An optical characterized by having one or more organic groups selected from the group of groups, substituted or unsubstituted aryl groups, and said that the reduced polymerization structure contains at least a Ti—O—Ti bond and a Si—O—Ti bond. It is a membrane.

A second aspect of the present invention is an optical device having a substrate provided with the optical film of the first aspect.

According to the present invention, an optical film having excellent transparency, antireflection and antifouling properties, which is applicable to optical devices such as optical panels such as solar panels and display devices and optical lenses such as surveillance cameras, is provided. A provided base material and an optical device having the base material can be provided.

[First aspect of the present invention]
The optical film according to the first aspect of the present invention includes (A) a low refractive index material exhibiting a refractive index of 1.22 to 1.32, and (B) a composite polymetalloxane. Here, the composite polymetalloxane acts as a binder, thereby forming a stable film containing the material. Further, the composite polymetalloxane contains a condensed polymerization structure of one or more metal alkoxides selected from the group consisting of alkoxytitanium and alkoxysilane, and the alkoxysilane of the composite polymetalloxane is at least a cationically polymerizable organic group. It has one or more organic groups selected from the group of saturated or unsaturated hydrocarbon groups having 1 to 21 carbon atoms and substituted or unsubstituted aryl groups. This polycondensation structure contains at least a Ti—O—Ti bond and a Si—O—Ti bond. Therefore, it functions as an antifouling material especially due to the Ti—O—Ti bond.
The thickness of the optical film is preferably 150 nm or less from the viewpoint of reflectance on the short wavelength side, and is preferably 90 nm or more from the viewpoint of reflectance on the long wavelength side. The thickness can be measured by using a spectroscopic ellipsometry method.

[(1) Low refractive index material]
The optical film contains a low refractive index material having a refractive index of 1.22 to 1.32 at a temperature of 23 ° C. for light having a wavelength of 589 nm. When the refractive index of the low-refractive material is larger than 1.32, the refractive index of the optical film at a temperature of 23 ° C. exceeds 1.40, and the refractive index becomes larger than the refractive index of 1.45 of the optical glass. Therefore, the anti-refractive performance is inferior, which is not preferable. When the refractive index of the low-refractive material is smaller than 1.22, the strength of the low-refractive material is weakened and the scratch resistance of the optical film is deteriorated, which is not preferable.

Specifically, as the low refractive index material, hollow particles, inorganic porous material particles, amorphous perfluororesin particles and the like are preferably used, but among them, hollow particles having a lower refractive index are most preferable.

As for the content of the low refractive index material in the optical film, light having a wavelength of 589 nm was incident on the optical film while considering the influence of other components such as polysiloxane and titanium oxide as the refractive index of the optical film at a temperature of 23 ° C. In some cases, the amount is preferably at least less than 1.38 [see also the weight ratio of the components contained in (2-6) and (2-7) below].

[(1-1) Hollow particles]
Hollow particles, which are preferred low refractive index materials, consist of particles having pores inside and shells around the outside of the pores. The refractive index of the antireflection film can be lowered by the air (refractive index 1.0) contained in the pores.

The material constituting the hollow particles is preferably a low refractive index, SiO _2, MgF _2, fluorine, including but organic resins such as silicone, SiO ₂ and more preferably is easy to produce the particles.

As a _{method for producing the hollow particles of SiO 2} , for example, it can be produced by the method described in Patent Document 5 or Patent Document 6.

The hollow particles make it possible to reduce the refractive index of a layer formed by stacking a plurality of particles aligned in a direction parallel to the surface of a base material.

As the average particle size of the hollow particles, it is preferable that the average particle size of the hollow particles is 15 nm from the viewpoint of stably forming the core particles. On the other hand, from the viewpoint of suppressing the generation of voids due to voids between particles and scattering due to the size of the particles, the average particle size of the hollow particles is preferably 100 nm or less, more preferably 60 nm or less.

Here, the average particle size of the hollow particles is the average ferret diameter. This average ferret diameter can be measured by image processing as observed by a transmission electron microscope image. As the image processing method, a commercially available image processing such as image Pro PLUS (manufactured by Media Cybernetics) can be used. In a predetermined image region, if necessary, the contrast is adjusted as appropriate, the average ferret diameter of each particle is measured by particle measurement, and the average value can be calculated and obtained.

The thickness of the shell of the hollow particles is preferably 10% or more, more preferably 15% or more of the average particle diameter from the viewpoint of particle strength; 50 from the viewpoint of effectively affecting the refractive index by the effect of hollow particles. % Or less is preferable, and 35% or less is more preferable.

[(1-2) Refractive index of low refractive index material (calculation method from film refractive index]
The refractive index of a low refractive index material, for example, hollow particles, is the refractive index (n) of an optical film formed only of low refractive index material particles and composite polymetallosane, and the refractive index of a film formed only of composite polymetallosane (n). The _{one calculated from n a} ) using the following formula (i) was used.

Equation (i): n = n _a φ _a + n _b φ _b
φ _a: Volume fraction of composite polymetallosane
φ _b: The volume fraction of the low refractive index material, which is _{a value obtained from 1-φ a.} Here, the refractive index of the optical film (n) and the refractive index of the film formed only of the composite polymetalloxane (n _a ). Shall use the value measured using the spectroscopic ellipsometry method. Hereinafter, the refractive index shall mean the refractive index at a temperature of 23 ° C. with respect to light having a wavelength of 589 nm, unless otherwise indicated.

Further, φ _a is calculated as 0.32 on the assumption that it is a body-centered cubic lattice, which is a general filling mode.

[(2) Composite polymetallosane]
In general, "polymetalloxane" is a polymer containing repeated metal-oxygen-metal bonds in a linear or network shape, and includes a polycondensation structure that can be obtained by a polycondensation reaction of a metal alkoxide. Further, the term "composite" is intended in the present application to be a metalloxane containing a plurality of metal atoms such as a titanium atom and a silicon atom as metal components. More specifically, the composite polymetalloxane referred to in the present invention contains a polycondensation structure of one or more metal alkoxides selected from the group consisting of alkoxysilane and alkoxytitanium, and the polycondensation structure is at least Ti-. Includes O-Ti bond and Si-O-Ti bond. Here, the polypolymerization structure of the metal alkoxide refers to a structure that can be obtained by the polypolymerization reaction of the metal alkoxide. Including the condensation reaction between the two, the condition that the polypolymerization structure contains at least a Ti—O—Ti bond and a Si—O—Ti bond can be satisfied.

Such a composite polymetalloxane can appropriately impart wear resistance, adhesion, and environmental reliability of an optical film as a binder, and can be used as an antifouling material due to the Ti—O—Ti bond in the condensed structure. Function.

Preferably, the composite polymetalloxane contains (A-1) polytitanoxane having a polycondensation structure of alkoxytitanium and (B-1) polytitanosiloxane having a polycondensation structure of alkoxysilane and alkoxytitanium. Moreover, polytitanoxane and polytitanosiloxane are condensed and bonded (Ti—O—Ti or Ti—O—Si bond) at least in part. Here, the polycondensation structure of alkoxytitanium refers to a structure (including a Ti—O—Ti bond) that can be obtained by a polycondensation reaction of alkoxysilane, and the polycondensation structure of alkoxysilane and alkoxytitanium is A structure (including at least a Si—O—Ti bond) that can be obtained by a polycondensation reaction of a mixture of alkoxysilane and alkoxytitanium. The Ti / Si molar ratio in the polytitanosiloxane is preferably in the range of 0.004 to 0.063 from the viewpoint of the refractive index.

Further, among such composite polymetallosanes, as described later in (2-1), after polycondensation of alkoxy titanium in advance, a mixture of alkoxy titanium and alkoxy silane is added to further polycondensation reaction. The composite polymetalloxane that can be obtained by carrying out the above is preferable from the viewpoint of antifouling property. It is presumed that the composite polymetallosane thus obtained may form a sea-island structure in which the polytitanoxane moiety is discontinuously mixed in the continuous polytitanosiloxane moiety.

Further, the composite polymetalloxane preferably forms a network structure by Si—O—Si bond, Ti—O—Ti bond, Ti—O—Si bond, etc., and the network structure can be strengthened by firing. can.

[(2-1) Preparation of composite polymetallosane]
As a preferred embodiment, alkoxytitanium is hydrolyzed / polycondensed to form polytitanoxane first, and then alkoxysilane and alkoxytitanium are further added to continue hydrolysis / polycondensation, thereby excellent in antifouling property. Complex polymetalloxane can be obtained. As described above, it is presumed that the composite polymetallosane thus obtained is composed of a polytitanoxane moiety and a polytitanosiloxane moiety, and the polytitanoxane moiety is considered to be effective in antifouling property.
More specifically, it is preferable to produce the pre-calcination polymer through the following steps (I) to (II).

That is,
(I) A step of mixing alkoxytitanium, water and alcohol and then hydrolyzing / polycondensating, and (II) adding alkoxysilane, alkoxytitanium, water and alcohol to the hydrolyzed / polycondensating solution. After that, the step of performing hydrolysis / polycondensation.

The following catalysts may be mixed in the steps (I) and (II).

・ Acid catalysts such as acetic acid, formic acid and hydrochloric acid,
・ Basic catalysts such as triethylamine and n-propylamine ・ Organic tin catalysts such as dibutyltin diacetate, dibutyltin bisacetylacetonate, dibutyltin bismaleic acid monobutyl ester, dioctyl bismaleic acid monobutyl ester ・ Bis (acetoxydibutyltin) oxide , Bis (lauroxydibutyltin) oxide and other organic tin oxide catalysts ・ Diisopropoxytitanium bis (acetylacetonate), titanium tetra (acetylacetonate), dioctanoxytitanium dioctanete, diisopropoxytitanium bis (ethylacetate) Titanium-based catalyst such as acetate) Further, in the step (I), one or more kinds of alkoxytitanium may be used in combination.

Further, in the step (II), one or more kinds of alkoxysilane and alkoxytitanium may be used in combination.

In step (I), the alkoxy group in the alkoxytitanium is converted to OH by hydrolysis, and further, by polycondensation between a plurality of OH groups, a linear or reticulated structure due to a Ti—O—Ti bond, preferably a reticulated structure. It is considered that the polymerization proceeds while forming the polytitanoxane to form the polytitanoxane (formation of the polytitanoxane moiety).

Similarly, in the step (II), the alkoxy group in the alkoxysilane and the alkoxytitanium is converted to OH by hydrolysis, and further polycondensation occurs between the plurality of OH groups. As a result, polymerization proceeds while forming a linear or reticulated structure, preferably a reticulated structure, formed by a Ti—O—Ti bond or a Ti—O—Si bond, and polytitanoxane formed in step (I) is surrounded by poly. It is presumed that titanosiloxane is formed (formation of polytitanosiloxane moiety). This Ti—O—Si bond includes not only the bond formed by the condensation between the alkoxysilane added in the step (II) and the alkoxytitanium, but also the uncondensed OH group in the polytitanoxane formed in the step (I). It is considered to include a bond formed by condensation with (condensation bond between polytitanoxane moiety and polytitanosiloxane moiety).

Further, the pre-calcination polymer, which is a composite polymetalloxane produced through the steps (I) to (II), is placed on the substrate during the film formation of the optical film (see [4] below) as described later. Is coated and fired. As a result, polycondensation by Si—O—Si bond, Ti—O—Ti bond, Ti—O—Si bond and the like is further promoted, and the linear or network structure is strengthened. Further, the crystal structure of the polytitanoxane moiety is not completely amorphous by the firing, but it is presumed to approach an anatase-type crystal structure having good antifouling property, which is advantageous from the viewpoint of antifouling property.

Such firing is preferably carried out under the condition of firing in an oven at a temperature of about 200 ° C. for about 2 hours. At this temperature, polycondensation proceeds further, but the organic groups derived from alkoxysilane are maintained.

By appropriately adjusting the amounts of the alkoxysilane and the alkoxytitanium used, a composite polymetalloxane having a more preferable structure can be obtained. It is presumed that such a structure may have a sea-island structure in which the polytitanoxane moiety is an island and the polytitanosiloxane moiety is a sea.

Since the composite polymetalloxane fired film has transparency even after the film is formed, it is also preferable in that transparency and antifouling property can be used together.

As the polytitanoxane moiety in the composite polymetallosane fired film, for example, a moiety _{containing TiO 4/2} units and containing a Ti—O—Ti bond can be exemplified.

Further, as the polytitanosiloxane portion in the composite polymetalloxane fired film, for example, one selected from the group consisting of ^{R 11} SiO _3/2 , R ³ SiO _3/2 and R ³ R ⁴ SiO _2/2. It is possible to exemplify a portion including the above first unit and a _{second unit which is a TiO 4/2} unit and including a Si—O—Si and a Si—O—Ti bond.

Here, R ¹¹ is a glycidyloxyalkyl group having 1 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, an epoxycycloalkyl group having 5 to 10 carbon atoms, more preferably 8 to 10 carbon atoms, or (epoxy). Cycloalkyl) Alkyl group. The epoxy ring-opening reaction may form a Ti—O—C or Si—OC bond (where C is a carbon atom derived from the epoxy ring) with the other unit.

R ³ and R ⁴ are saturated or unsaturated hydrocarbon groups having 1 to 21 carbon atoms, preferably 6 to 10 carbon atoms, preferably substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups. .. As the alkyl group, a linear alkyl group having 1 to 21 carbon atoms is preferable, and a linear alkyl group having 6 to 10 carbon atoms is more preferable. As the aryl group, preferably, an aryl group having 6 to 10 carbon atoms, for example, a phenyl group and the like can be mentioned. Examples of the substituent of the alkyl group or the aryl group include a phenyl group and the like.

In this case, the polytitanoxane moiety and the polytitanosiloxane moiety are preferably linked by a Ti—O—Si bond and / or a Ti—O—Ti bond.

The notation of O _4/2 , O _3/2 , O _{2/2, etc. is two Si-O 1/2} units, for example, taking the combination of Si-O-Si and Si-O-Ti as an example. It is a notation derived from the combination of Si-O _1/2 unit and Ti-O _{1/2 unit.} Therefore, for example ^{, the notation R 3} R ⁴ SiO _2/2 means a combination with two other Si-O _1/2 or Ti-O _{1/2 units.}

[(2-2) Alkoxy Titanium]
Suitable alkoxytitanium as a raw material for the composite polymetallosane is, for example, the formula (ii):
Ti (OR ²¹ ) ₄ (ii)
(In the formula, R ²¹ is the same or different and represents a saturated or unsaturated hydrocarbon group.)
One or more of can be mentioned.

More specifically, titanium tetraethoxydo, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra t-butoxide and the like can be mentioned. These can be used alone or in combination of two or more.

[(2-3) Alkoxysilane]
Next, as a suitable alkoxysilane as a raw material of the composite polymetallosane, for example, any one or more of the following formulas (iii) to (vi) can be mentioned. Among these, from the viewpoint of film forming property, it is preferable that at least a part of the alkoxysilane used is of the formulas (iii) and / or (iv) because it promotes the formation of a network structure.
Equation (iii):
R ¹ −Si− (OR ² ) ₃ (iii)
[In the above formula (iii), R ¹ is a cationically polymerizable organic group, for example, a glycidyloxyalkyl group having 1 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, or 5 to 10 carbon atoms, more preferably. An epoxycycloalkyl group or a (epoxycycloalkyl) alkyl group having 8 to 10 carbon atoms is shown. R ² represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, preferably 6 to 10 carbon atoms. ]
Equation (iv):
(R ³ ) ₁ −Si− (OR ² ) ₃ (iv)
[In the above formula (iv), R ³ is a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, preferably 6 to 10 carbon atoms, preferably a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. It is an aryl group of. As the alkyl group, a linear alkyl group having 1 to 21 carbon atoms is preferable, and a linear alkyl group having 6 to 10 carbon atoms is more preferable. As the aryl group, preferably, an aryl group having 6 to 10 carbon atoms, for example, a phenyl group and the like can be mentioned. Examples of the substituent of the alkyl group or the aryl group include a phenyl group and the like. R ² represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, preferably 6 to 10 carbon atoms]
Equation (v):
(R ³ ) _2- Si- (OR ² ) ₂ (v)
[In the above formula (v), R ³ is a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, preferably 6 to 10 carbon atoms, preferably a substituted or unsubstituted alkyl group, or a substituted or substituted alkyl group. It is an unsaturated aryl group. As the alkyl group, a linear alkyl group having 1 to 21 carbon atoms is preferable, and a linear alkyl group having 6 to 10 carbon atoms is more preferable. As the aryl group, preferably, an aryl group having 6 to 10 carbon atoms, for example, a phenyl group and the like can be mentioned. Examples of the substituent of the alkyl group or the aryl group include a phenyl group and the like. R ² represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, preferably 6 to 10 carbon atoms]
Equation (vi):
(R ³ ) (R ⁴ ) -Si- (OR ² ) ₂ (vi)
[In the above formula (vi), R ³ and R ⁴ are saturated or unsaturated hydrocarbon groups having 1 to 21 carbon atoms, preferably 6 to 10 carbon atoms, preferably substituted or unsubstituted alkyl groups, or , Substituted or unsubstituted aryl group. As the alkyl group, a linear alkyl group having 1 to 21 carbon atoms is preferable, and a linear alkyl group having 6 to 10 carbon atoms is more preferable. As the aryl group, preferably, an aryl group having 6 to 10 carbon atoms, for example, a phenyl group and the like can be mentioned. Examples of the substituent of the alkyl group or the aryl group include a phenyl group and the like. R ² represents a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, preferably 6 to 10 carbon atoms]
Specific examples of the formula (iii) include the following compounds.
-3-Glysidyloxypropyltrimethoxysilane-3-Glysidyloxypropyltriethoxysilane-2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane-2- (3,4-epoxycyclohexyl) ethyltriethoxysilane formula ( Specific examples of iv) include the following compounds.
-Methyltrimethoxysilane-Methyltriethoxysilane-Methyltripropoxysilane-Ethyltrimethoxysilane-Ethyltriethoxysilane-Ethyltripropoxysilane-propyltrimethoxysilane-propyltriethoxysilane-propyltripropoxysilane-Hexyltrimethoxysilane・ Hexyltriethoxysilane ・ Hexyltripropoxysilane ・ Octyltrimethoxysilane ・ Octyltriethoxysilane ・ Octyltrimethoxysilane ・ Decyltrimethoxysilane ・ Decyltriethoxysilane ・ Decyltripropoxysilane ・ Phenyltrimethoxysilane ・ Phenyltriethoxysilane -Specific examples of the phenyltripropoxysilane formula (v) include the following compounds.
-Didimethyldimethoxysilane-Didimethyldiethoxysilane-Dimethyldipropoxysilane-Diisopropyldimethoxysilane-Methoxysilane-Diphenyldiethoxysilane-Diphenyldipropoxysilane Specific examples of the formula (vi) include the following compounds.
-Methylphenyldimethoxysilane-Methylphenyldiethoxysilane-Methylphenyldipropoxysilane [(2-4) Titanium atom content in each part]
^{The titanium atom contents a 1} and a ² in the composite polymetalloxane fired film can be calculated by the following formulas (vi) and (vi).

a ¹ (mol%) = {α / (α + β + γ)} × 100 (vii)
a ² (mol%) = {β / (α + β + γ)} × 100 (viii)
Here, a ¹ is the content rate (mol%) of titanium atoms (Ti) contained in the polytitanoxane moiety based on the amount (mol) of all metal atoms (Ti + Si) of the optical film. Further, a ² is the content rate (mol%) of titanium atoms (Ti) contained in the polytitanosiloxane portion based on the amount (mol) of all metal atoms (Ti + Si) of the optical film.

The number of moles of alkoxytitanium used when synthesizing the polytitanoxane moiety was α (molar), and the number of moles of alkoxytitanium and alkoxysilane used when synthesizing the polytitanosiloxane moiety were β (molar) and γ (mole), respectively. Mol).

Next, from the viewpoint of good antifouling property, the ratio a ¹ / a ² is preferably 2 or more.
That is, the following equation (ix):
2 ≤ a ¹ / a ² (ix)
It is preferable to satisfy.

Further, from the viewpoint of good antifouling property, a ¹ is preferably 6.25 or more, and from the viewpoint of maintaining good antireflection performance and transmittance, it is preferably 53 or less. ^{On the other hand, a 2} is preferably 0.50 or more from the viewpoint of uniform dispersion of titanium atoms in the polytitanosiloxane partial region at the time of film formation, prevention of lump formation, and uniform antifouling property. Further, from the viewpoint of good adhesion between the base material and the low refractive index material, prevention of peeling of the low refractive index material, and wear resistance of the film, a ² is preferably 6.25 or less.
That is, it is preferable to satisfy the following formulas (ix) and (x), respectively.
6.25 ≤ a ¹ ≤ 53 (x)
0.50 ≤ a ² ≤ 6.25 (xi)

[(2-5) Infrared absorption intensity of Ti-O-Ti / Si-O-Ti (A ¹ and A ² )]
Quantitative analysis by infrared spectroscopy can be used to estimate the absorption intensity A ^{1 of the absorption band 840 cm -1} derived from the Ti—O—Ti bond contained in the composite polymetalloxane. Similarly, the absorption intensity A ^{2 of the absorption band 950 cm -1} derived from the Si—O—Ti bond contained in the composite polymetalloxane can be estimated by the quantitative analysis of infrared spectroscopy.

Then, from the viewpoint of sufficiently securing the ratio of the polytitanoxane portion in the composite polymetallosane fired film of the present invention and obtaining good antifouling property, ^{it is preferable that A 1} / A ² is 2 or more. That is, it is preferable to satisfy the following formula (xii).
2 ≤ A ¹ / A ² (xii)
In the present invention, if the reaction of the polytitanoxane moiety and the subsequent reaction of the polytitanosiloxane moiety proceed almost completely, this condition is considered to be substantially equivalent to the condition of the formula (viii) of the above formula (2-4). In this case, the Ti—O—Ti content of the polytitaniumoxane moiety and the Si—O—Ti content of the polytitaniumsiloxane moiety match the amount of the reagent set. In fact, in the examples, the a ¹ / a ^{2 ratio in Table 1} and the A 1 / A ² ratio in Table 2 have the same values in all the examples and comparative examples. That is, in this case, it is considered that the absorption intensity A1 is derived from the Ti—O—Ti bond of the polytitanoxane moiety, and the absorption intensity A2 is derived from the Si—O—Ti bond of the polytitanosiloxane moiety.

[(2-6) Weight ratio of composite polymetallosane fired film to low refractive index material]
When the content of the low refractive index material is b and the content of the composite polymetalloxane fired film is c, b / c is preferably 0.18 or more from the viewpoint of good antireflection performance and transmittance. .. On the other hand, b / c is preferably 61 or less from the viewpoint of preventing peeling of low-refractive material particles, abrasion resistance of the film, and antifouling property.

That is, it is preferable to satisfy the following formula (xiii).
0.18 ≤ b / c ≤ 61 (xiii)
Here, when low refractive index particles are used in any intermediate layer described in (3) below, the weight thereof is not included in the above b.

[(2-7) Additional antifouling material particles]
The composite polymetalloxane fired film may further optionally contain antifouling material particles such as titanium oxide particles. Compared to the case where only antifouling material particles such as titanium oxide particles are used as the antifouling material, the amount of antifouling material particles such as titanium oxide can be reduced, and a low refractive index is achieved while maintaining antifouling properties. It is preferable in that it can be done.

Further, the titanium oxide particles are preferably titanium oxide particles that can take a crystal system, and the crystal system of the titanium oxide particles is more preferably anatase type. The anatase type is preferable because it has a higher catalytic activity ability than the rutile type and photocatalytic superhydrophilicity, that is, superhydrophilicity is exhibited by irradiation with ultraviolet rays, so that the antifouling effect is enhanced.

From the viewpoint of good reflectance / transmittance and transparency, the average particle size of the titanium oxide particles is preferably 100 nm or less, more preferably 60 nm or less, and further preferably 50 nm or less. On the other hand, from the viewpoint of facilitating the formation of anatase type, which is a crystal system having better antifouling property, the average particle size of titanium oxide particles is preferably 1 nm or more.

The average particle size of the titanium oxide particles can be measured by using a laser diffraction method. More specifically, a laser diffraction method using a nanoparticle particle size distribution measuring instrument (trade name "UPA-EX250", manufactured by Nikkiso Co., Ltd.) can be used. Most ambiguously, it may be obtained by a method by an X-ray diffraction method.

Further, the content d of the additional antifouling material particles is such that the content b of the low refractive index material and the content c of the composite polymetallosane fired film are as follows from the viewpoint of maintaining the transmittance, power generation efficiency, and reflection performance. It is preferable to satisfy the relationship (xiv).
d / (b + c + d) ≤ 0.1 (xiv)
Here, when low refractive index particles are used in any intermediate layer described in (3) below, the weight thereof is not included in the above b.

[(3) Middle layer]
The optical film of this embodiment may further optionally include an intermediate layer. In particular, when hollow particles are used as the low refractive index material, the adhesion of the optical film to the substrate can be improved by providing an intermediate layer containing the non-hollow particles.

As the non-hollow particles constituting such an intermediate layer, low refractive index particles having a refractive index of 1.20 to 1.40 (25 ° C., sodium D line) are preferable from the viewpoint of low refractive index and antireflection performance. More specifically, inorganic oxides such as _{ZrO 2 and} Al ₂ O _{3 and inorganic compounds such as MgF 2} are preferable, and MgF ₂ is particularly preferable. However, it is preferable to adjust the refractive index and the amount used of the non-hollow particles so as not to impair the original antireflection performance of the optical film provided with the intermediate layer.

The average particle size of the inorganic oxide or inorganic compound used in the intermediate layer is preferably 150 nm or less, more preferably 50 nm or less from the viewpoint of transmittance.

[(4) Method for forming an optical film]
The optical film is formed on the surface of the base material or, if an intermediate layer is provided, on the intermediate layer after the low refractive index material dispersion liquid is applied, and then the composite polymetalloxane (polymer before firing). A method having a step of further coating the compounding solution and drying / firing is preferable. Therefore, the optical film of the first aspect of the present invention is usually produced in the form of a base material provided with the optical film.

As a result, the composite polymetalloxane as a binder is inserted between the low refractive index materials, and an optical film containing the low refractive index material can be obtained. By going through the firing step, the condensation of the composite polymetalloxane further progresses and the film forming property is improved.

When additional antifouling material particles are also used, for example, a composite polymetalloxane containing additional antifouling material particles can be used by using a preparation solution previously added to the composite polymetallosane (pre-baking polymer) preparation solution. A fired film can be obtained.

Here, the base material is preferably a transparent base material, typically a glass base material.

As the coating method, a wet process such as a dipping method, a spin coating method, a spray method, a printing method, or a flow coating method can be used. However, the method for forming an optical film is not limited to these methods.

Further, when an intermediate layer is optionally provided, as a method for forming the intermediate layer, a method using a dry process or a method having a step of coating after coating by a wet process and then drying can be used. As the former, a vacuum vapor deposition method in which an inorganic oxide or an inorganic compound is heated to be melted / evaporated or sublimated, and the evaporated / sublimated particles are adhered / deposited on the surface of a substrate to form a film can be exemplified. Examples of the latter include a method of applying a film-forming liquid containing an inorganic oxide, an inorganic compound, or a solvent onto the surface of a substrate by a dipping method, a spin coating method, a spray method, a printing method, a flow coating method, or the like. can.

[(5) Optical device having a base material provided with an optical film]
The optical device according to the second aspect of the present invention includes the optical film according to the first aspect of the present invention on the base material thereof or on an intermediate layer arbitrarily formed on the base material.

Examples of the optical device include a solar panel, a display device, an optical lens, and the like. Here, examples of the display device include a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display device (LCD). Further, examples of the optical lens include optical lenses for surveillance cameras and telescopes.

By applying the optical film of the first aspect of the present invention to these optical devices, in the solar panel, the power generation efficiency is improved by the antireflection function, and the antifouling property of the panel stains such as bird manure, dust, and water stains. Alternatively, a self-cleaning function can be given to the panel surface. Further, the display device can deal with problems such as a decrease in contrast due to reflection of external light, reflection of an image, and contamination of the display surface. Further, the optical lens can deal with the problem of image blurring due to image reflection and stains due to adhesion of hand stains, fingerprints, and the like.

When the optical film includes an intermediate layer which is an arbitrary layer, the intermediate layer is arranged between the base material of the optical device and the optical film.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

It should be noted that those described as "parts" and "%" regarding the amount of components are based on weight unless otherwise specified.

The structural parts of the synthesized sol and ^{polymetalloxane were identified using 1} H-NMR and ²⁹ Si-NMR (nuclear magnetic resonance apparatus, trade name "ECA400", manufactured by JEOL Ltd.). The solid content was measured using the dry weight loss method. The average particle size was measured using a laser diffraction method using a nanoparticle particle size distribution measuring device (trade name "UPA-EX250", manufactured by Nikkiso Co., Ltd.).

[(I) Preparation of low refractive index material dispersion liquid]
[Preparation of (I-1) Hollow Silica Particle Dispersion Liquid 1]
Hollow silica slurry IPA dispersion (Thruria 1110 manufactured by JGC Catalysts and Chemicals Co., Ltd., average ferret diameter 55 nm, solid content concentration 20.5% by weight, refractive index of hollow silica particle material itself: 1.30, the hollow silica particles It may be referred to as "hollow silica particles 1".) 4.5 parts by weight of 1-ethoxy-2-propanol was placed in a 100 ml eggplant flask of 9.00 parts by weight. It was then concentrated on an evaporator and the solvent was replaced with 1-ethoxy-2-propanol. Then, 11.0 parts by weight of 1-ethoxy-2-propanol and 15.0 parts by weight of 1-butoxy-2-propanol were added, and 13.5 parts by weight of 2-ethylbutanol was added to make 1.9% by weight of hollow silica particles. The dispersion liquid 1 was prepared.

[Preparation of (I-2) Porous MgF ₂ Precursor Dispersion Liquid]
6.90 parts by weight of magnesium diethoxydo, 38.2 parts by weight of 2-ethylbutanol, was placed in a 500 ml eggplant flask, stirred at room temperature, and 6.90 parts by weight of trifluoroacetic acid was added dropwise. Then, stirring was performed for 3 hours. Then, after filtering under reduced pressure, it was dried under heating and vacuum at 100 ° C. for 2 hours to obtain magnesium trifluoroacetate which is _{a porous MgF 2 precursor.}

To 5 parts by weight of this magnesium trifluoroacetate, 53 parts by weight of 1-ethoxy-2-propanol and 39 parts by weight of 1-butoxy-2-propanol were added. As a result, a 3.8% by weight porous MgF ₂ precursor dispersion was prepared.

This porous MgF _{2 precursor is converted into porous MgF 2} particles (non-hollow, refractive index 1.25) at the time of firing at the time of forming an optical film.

[Preparation of (I-3) non-hollow SiO ₂ dispersion liquid]
The following ingredients were placed in a 100 ml eggplant flask.

・ 30% by weight organosilica sol (methanol silica sol manufactured by Nissan Chemical Industry Co., Ltd.) 2.8 parts by weight ・ 1-ethoxy-2-propanol 8.0 parts by weight ・ 1-butoxy-2-propanol 6.0 parts by weight ・ 2- 6.0 parts by weight of ethyl butanol Then, the mixture was stirred at room temperature to prepare _{a 3.8% by weight non-hollow SiO 2 dispersion.}

The refractive index of the SiO ₂ particle material itself was 1.46.

[Preparation of (I-4) Hollow Silica Particle Dispersion Liquid 2]
<Hollow silica particles 2>
0.19 g of stearyltrimethylammonium chloride was dissolved in 200 ml of water while heating, and the temperature was raised to 80 ° C. After adding 2 ml of styrene monomer and stirring, 0.6 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added. The reaction was completed by stirring for 3 hours as it was, and polystyrene particles were obtained. Next, 100 ml of the reaction solution obtained by completing the above reaction was separated, 10 g of 2-ethylbutanol was added, and the mixture was stirred at room temperature. Further, after adding 3.0 g of triethoxymethylsilane, the mixture was stirred for 40 hours to precipitate and coat silica around the polystyrene particles. Further, centrifugation and washing were repeated to remove impurities other than core-shell particles to obtain a dispersion of core-shell particles. The core-shell particles were heated from room temperature to 600 ° C. under the condition of 10 ° C./min under an air atmosphere, and held at 600 ° C. for 3 hours. Then, the mixture was cooled to room temperature at a rate of 10 ° C./min to prepare hollow silica particles 2 (refractive index 1.22).
<Hollow silica particle dispersion liquid 2>
Then, 11.0 parts by weight of 1-ethoxy-2-propanol and 15.0 parts by weight of 1-butoxy-2-propanol were added to 0.75 parts by weight of the hollow silica particles 2, and 13.5 parts by weight of 2-ethylbutanol was added. Then, 1.9% by weight of the hollow silica particle dispersion liquid 2 was prepared.

[Preparation of (I-5) Hollow Silica Particle Dispersion Liquid 3]
<Hollow silica particles 3>
Hollow silica particles 3 (refractive index 1.32) were produced in the same manner as the hollow silica particles 2 described above, except that the amount of triethoxymethylsilane was changed to 7.6 g.
<Hollow silica particle dispersion liquid 3>
A 1.9% by weight hollow silica particle dispersion liquid 3 was prepared in the same manner as the above-mentioned hollow silica particle dispersion liquid 2 except that the hollow silica particles 2 were changed to the hollow silica particles 3.

[Preparation of (I-6) Hollow Silica Particle Dispersion Liquid 4]
<Hollow silica particles 4>
Hollow silica particles 4 (refractive index 1.21) were produced in the same manner as the hollow silica particles 2 described above, except that the amount of triethoxymethylsilane was changed to 2.7 g.
<Hollow silica particle dispersion liquid 4>
A 1.9% by weight hollow silica particle dispersion liquid 4 was prepared in the same manner as the above-mentioned hollow silica particle dispersion liquid 2 except that the hollow silica particles 2 were changed to the hollow silica particles 4.

[Preparation of (I-7) Hollow Silica Particle Dispersion Liquid 5]
<Hollow silica particles 5>
Hollow silica particles 5 (refractive index 1.33) were produced in the same manner as the hollow silica particles 2 described above, except that the amount of triethoxymethylsilane was changed to 8.7 g.
<Hollow silica particle dispersion liquid 5>
A 1.9% by weight hollow silica particle dispersion liquid 5 was prepared in the same manner as the above-mentioned hollow silica particle dispersion liquid 2 except that the hollow silica particles 2 were changed to the hollow silica particles 5.

[(II) Preparation of pre-calcination polymer formulation]
Hereinafter, the preparation of various pre-calcination polymer preparations for the production of composite polymetallosane will be disclosed.

[(II-1) Preparation of Pre-Baking Polymer 1 and Formulation A]
<Polymer before firing 1>
In a water bath set at 25 ° C., put 8 parts by weight (28 mmol) of titanium tetraisopropoxide, 20 parts by weight of 2-butanol, and 1 part by weight of hydrochloric acid in a 300 ml eggplant flask and stir, and add 10 parts by weight of ion-exchanged water. It was added while dropping a portion. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 0.8 parts by weight (2.9 mmol)
-36.0 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain 18% by weight of a pre-calcination polymer 1 solution.
<Formulation liquid A>
Next, 123 parts by weight of 2-ethylbutanol was added to 1 solution of the pre-calcination polymer by 5 parts by weight and stirred to obtain 0.7% by weight of the pre-calcination polymer 1 preparation solution A.

[(II-2) Preparation of Pre-Baking Polymer 2 and Formulation B]
<Polymer before firing 2>
In a water bath set at 25 ° C., put 8 parts by weight (28 mmol) of titanium tetraisopropoxide, 20 parts by weight of 2-butanol, and 1 part by weight of hydrochloric acid in a 300 ml eggplant flask and stir, and add 10 parts by weight of ion-exchanged water. It was added while dropping a portion. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

-Didimethyldimethoxysilane 1.71 parts by weight (14 mmol)
21.1 parts by weight (87 mmol) of dimethoxydiphenylsilane
-Titanium tetraisopropoxide 0.8 parts by weight (2.9 mmol)
-33.7 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 15% by weight pre-calcination polymer 2 solution.
<Formulation B>
Next, 101 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 2 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 2 preparation solution B.

[(II-3) Preparation of Pre-Baking Polymer 3 and Formulation C]
<Polymer before firing 3>
In a water bath set at 25 ° C., put 8 parts by weight (28 mmol) of titanium tetraisopropoxide, 20 parts by weight of 2-butanol, and 1 part by weight of hydrochloric acid in a 300 ml eggplant flask and stir, and add 10 parts by weight of ion-exchanged water. It was added while dropping a portion. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

-Bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane 26 parts by weight (84 mmol)
-0.8 parts by weight (2.9 mmol) of titanium tetraisopropoxide
-33.7 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 19% by weight pre-calcination polymer 3 solution.
<Formulation C>
Next, 128 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 3 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 3 preparation solution C.

[(II-4) Preparation of Pre-Baking Polymer 4 and Formulation D]
<Polymer before firing 4>
In a water bath set at 25 ° C., put 1.8 parts by weight (6.25 mmol) of titanium tetraisopropoxide, 4.5 parts by weight of 2-butanol, and 0.2 parts by weight of hydrochloric acid in a 300 ml eggplant flask and stir. Then, 2.2 parts by weight of ion-exchanged water was added while dropping. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 0.14 parts by weight (0.5 mmol)
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain 24% by weight of 4 solutions of the pre-calcination polymer.
<Formulation liquid D>
Next, 164 parts by weight of 2-ethylbutanol was added to 4 solutions of the polycondensate in an amount of 5 parts by weight and stirred to obtain 0.7% by weight of a pre-calcination polymer 4 preparation solution D.

[(II-5) Preparation of Pre-Baking Polymer 5 and Formulation E]
<Polymer before firing 5>
In a water bath set at 25 ° C., put 3.6 parts by weight (12.5 mmol) of titanium tetraisopropoxide, 9 parts by weight of 2-butanol, and 0.4 parts by weight of hydrochloric acid in a 300 ml eggplant flask and stirred. Ion-exchanged water was added while dropping 4.4 parts by weight. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 1.78 parts by weight (6.3 mmol)
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 22% by weight pre-calcination polymer 5 solution.
<Formulation liquid E>
Next, 151 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 5 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 5 preparation solution E.

[(II-6) Preparation of Pre-Baking Polymer 6 and Formulation F]
<Polymer before firing 6>
In a water bath set at 25 ° C., put 1.8 parts by weight (6.25 mmol) of titanium tetraisopropoxide, 4.5 parts by weight of 2-butanol, and 0.2 parts by weight of hydrochloric acid in a 300 ml eggplant flask and stir. Then, 2.2 parts by weight of ion-exchanged water was added while dropping. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
0.88 parts by weight (3.1 mmol) of titanium tetraisopropoxide
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain 24% by weight of 6 pre-calcination polymer solutions.
<Formulation liquid F>
Next, 164 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the polycondensate solution 6 and stirred to obtain 0.7% by weight of the pre-calcination polymer 6 preparation solution F.

[(II-7) Preparation of Pre-Baking Polymer 7 and Formulation G]
<Polymer before firing 7>
In a water bath set at 25 ° C., put 15.1 parts by weight (53 mmol) of titanium tetraisopropoxide, 45 parts by weight of 2-butanol and 2.2 parts by weight of hydrochloric acid in a 300 ml eggplant flask, and stir to exchange ions. Water was added while dropping 22.3 parts by weight. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 0.14 parts by weight (0.5 mmol)
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 14% by weight pre-calcination polymer 7 solution.
<Formulation liquid G>
Next, 97 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 7 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 7 preparation solution G.

[(II-8) Preparation of Pre-Baking Polymer 8 and Formulation H]
<Polymer before firing 8>
In a water bath set at 25 ° C., put 15.1 parts by weight (53 mmol) of titanium tetraisopropoxide, 45 parts by weight of 2-butanol and 2.2 parts by weight of hydrochloric acid in a 300 ml eggplant flask, and stir to exchange ions. Water was added while dropping 22.3 parts by weight. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 1.78 parts by weight (6.25 mmol)
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 15% by weight pre-calcination polymer 8 solution.
<Formulation H>
Next, 99 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 8 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 8 preparation solution H.

[(II-9) Preparation of Formulation I of Pre-Baking Polymer 1]
4 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 1 solution and stirred to obtain 10.5% by weight of the pre-baking polymer 1 preparation solution I.

[(II-10) Preparation of Formulation J of Pre-Baking Polymer 1]
682 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 1 solution and stirred to obtain 0.13% by weight of the pre-baking polymer 1 preparation solution J.

[(II-11) Preparation of Pre-Baking Polymer 9 and Formulation K]
<Polymer before firing 9>
In a water bath set at 25 ° C., put 1.8 parts by weight (6.25 mmol) of titanium tetraisopropoxide, 4.5 parts by weight of 2-butanol, and 0.2 parts by weight of hydrochloric acid in a 300 ml eggplant flask and stir. Then, 2.2 parts by weight of ion-exchanged water was added while dropping. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 1.78 parts by weight (6.25 mmol)
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Was added while dropping. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 24% by weight pre-calcination polymer 9 solution.
<Formulation K>
Next, 164 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 9 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 9 preparation solution K.

[(II-12) Preparation of Pre-Baking Polymer 10 and Formulation L]
<Polymer 10 before firing>
In a water bath set at 25 ° C., put 15.1 parts by weight (53 mmol) of titanium tetraisopropoxide, 46 parts by weight of 2-butanol, and 2.3 parts by weight of hydrochloric acid in a 300 ml eggplant flask, and stir to exchange ions. Water was added while dropping 23.1 parts by weight. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 1.78 parts by weight (6.25 mmol)
-8 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 17% by weight pre-calcination polymer 10 solution.
<Formulation liquid L>
Next, 117 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 10 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 10 preparation solution L.

[(II-13) Preparation of Pre-Baking Polymer 11 and Formulation M]
<Polymer before firing 11>
In a water bath set at 25 ° C., 1.7 parts by weight (6 mmol) of titanium tetraisopropoxide, 4.5 parts by weight of 2-butanol and 0.2 parts by weight of hydrochloric acid were placed in a 300 ml eggplant flask and stirred. Ion-exchanged water was added while dropping 2.2 parts by weight. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
0.82 parts by weight (2.9 mmol) of titanium tetraisopropoxide
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 24% by weight pre-calcination polymer 11 solution.
<Formulation liquid M>
Next, 164 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 11 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 11 preparation solution M.

[(II-14) Preparation of Pre-Baking Polymer 12 and Formulation N]
<Polymer before firing 12>
In a water bath set at 25 ° C., put 8.0 parts by weight (28 mmol) of titanium tetraisopropoxide, 20 parts by weight of 2-butanol and 1 part by weight of hydrochloric acid in a 300 ml eggplant flask, and stir to add ion-exchanged water. It was added while dropping 10 parts by weight. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 0.11 part by weight (0.4 mmol)
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain 18% by weight of 12 pre-calcination polymer solutions.
<Formulation liquid N>
Next, 126 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 12 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 12 preparation solution N.

[(II-15) Preparation of Pre-Baking Polymer 13 and Formulation O]
<Polymer before firing 13>
In a water bath set at 25 ° C., put 8.0 parts by weight (28 mmol) of titanium tetraisopropoxide, 20 parts by weight of 2-butanol and 1 part by weight of hydrochloric acid in a 300 ml eggplant flask, and stir to add ion-exchanged water. It was added while dropping 10 parts by weight. Then, stirring was performed for 3 hours.

Then, the following components were added and stirred.

3.35 parts by weight (14 mmol) of 3-glycidyloxypropyltrimethoxysilane
Octiltriethoxysilane 23.9 parts by weight (86 mmol)
-Titanium tetraisopropoxide 1.79 parts by weight (6.3 mmol)
-34 parts by weight of 2-butanol Then, 3.25 parts by weight of ion-exchanged water was added dropwise thereto. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain 18% by weight of the pre-calcination polymer 13 solution.
<Formulation liquid O>
Next, 127 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 13 solution and stirred to obtain 0.7% by weight of the pre-baking polymer 13 preparation solution O.

[(II-16) Preparation of Formulation P of Pre-Baking Polymer 1]
0.8 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 1 solution and stirred to obtain 15.5% by weight of the pre-baking polymer 1 preparation solution P.

[(II-17) Preparation of Formulation Q for 1 Solution of Pre-Baking Polymer]
727 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the pre-baking polymer 1 and stirred to obtain 0.12% by weight of the pre-baking polymer 1 preparation liquid Q.

[(II-18) Preparation of Pre-Bake Polymer 1 / Titanium Oxide Particle Formulation R]
75 parts by weight of 2-ethylbutanol, 30% by weight titanium oxide ST01 (average particle diameter 7 nm manufactured by Ishihara Sangyo Co., Ltd.) was added and stirred by 1.8 parts to obtain 0.7% by weight titanium oxide particle dispersion liquid 1.

Next, 0.05 parts by weight of the obtained titanium oxide particle dispersion 1 was added to 0.3 parts by weight of the pre-baking polymer 1 preparation liquid A, and the pre-firing polymer 1 / titanium oxide particle preparation was added. R was obtained.

[Preparation of (II-19) Polysiloxane Comparative Formulation S]
In a 300 ml eggplant flask in a water bath set at 25 ° C., 3.35 parts by weight (14 mmol) of 3-glycyloxypropyltrimethoxysilane, 23.9 parts by weight (86 mmol) of octylriethoxysilane, 2-butanol. 34 parts by weight was added and stirred. To this, 3.25 parts by weight of ion-exchanged water was added while dropping. Then, the flask was placed in an oil bath set at 120 ° C., stirred, and heated under reflux for 3 hours to obtain a 26 wt% polysiloxane 14 solution.

Next, 180 parts by weight of 2-ethylbutanol was added to 5 parts by weight of the polysiloxane 14 solution and stirred to obtain 0.7% by weight of the polysiloxane comparative preparation liquid S.

[(III) Preparation of preparation liquid for intermediate layer formation]
6.90 parts by weight of magnesium diethoxydo, 38.2 parts by weight of 2-ethylbutanol and 1.00 parts by weight of acetylacetone were placed in a 100 ml eggplant flask and stirred at room temperature. Then, 6.90 parts by weight of trifluoroacetic acid was added dropwise and stirred to obtain a 26% by weight magnesium acetate sol solution.

To this magnesium acetate sol solution, 139 parts by weight of 1-ethoxy-2-propanol and 104 parts by weight of 1-butoxy-2-propanol were added, and 66.3 parts by weight of 2-ethylbutanol was added. As a result, a 3.8% by weight trifluoromagnesium acetate sol solution, which was a preparation solution for forming an intermediate layer, was obtained.

[(IV) Manufacture of optical film]
[(IV-1) Example 1: Optical film 1]
The substrate (slide glass water edge polishing material: soda glass square 3 (thickness) × 40 × 40 mm) was ultrasonically cleaned with isopropyl alcohol for 30 minutes and dried. Then, dust was removed by ozone cleaning for 30 minutes and a substrate cleaning spray to obtain a coating glass substrate.

On this coating glass substrate, 0.3 ml of the trifluoromagnesium acetate sol solution, which is a preparation solution for forming an intermediate layer, was applied using a spin coating device (trade name: "1HD7", manufactured by Mikasa Co., Ltd.). Spin coating was performed at a rotation speed of 2000 rpm for 90 seconds. Then, it was calcined at 250 ° C. for 2 hours. By such firing, magnesium trifluoroacetate _{is converted into porous MgF 2} particles (non-hollow, refractive index 1.25). Further, 0.3 ml of the hollow silica particle dispersion liquid 1 is spin-coated on this film. Using the device, spin coating was performed at a rotation speed of 2685 rpm for 60 seconds. Next, 0.3 ml of the pre-baking polymer 1 preparation solution A was spin-coated at a rotation speed of 2685 rpm for 60 seconds using a spin coating device, and fired at 200 ° C. for 2 hours to produce an optical film 1.

[(IV-2) Example 2: Optical Film 2]
The optical film 2 was produced in the same manner as in Example 1 described above, except that the pre-sintering polymer 1 preparation liquid A was changed to the pre-sintering polymer 2 preparation liquid B.

[(IV-3) Example 3: Optical Film 3]
The optical film 3 was produced in the same manner as in Example 1 described above, except that the pre-sintering polymer 1 preparation liquid A was changed to the pre-sintering polymer 3 preparation liquid C.

[(IV-4) Example 4: Optical Film 4]
The substrate (slide glass water edge polishing material: soda glass square 3 (thickness) × 40 × 40 mm) was ultrasonically cleaned with isopropyl alcohol for 30 minutes and dried. Then, dust was removed by ozone cleaning for 30 minutes and a substrate cleaning spray to obtain a coating glass substrate.

On this coating glass substrate, _{0.3 ml of the porous MgF 2} precursor dispersion liquid was spin-coated at a rotation speed of 2685 rpm for 60 seconds using a spin coating device. Next, 0.3 ml of the pre-baking polymer 1 preparation solution A was spin-coated at a rotation speed of 2685 rpm for 60 seconds using a spin coating device, and fired at 200 ° C. for 2 hours to produce an optical film 4.

[(IV-5) Example 5: Optical film 5]
The optical film 5 was produced in the same manner as in Example 1 described above, except that the pre-sintering polymer 1 preparation liquid A was changed to the pre-sintering polymer 4 preparation liquid D.

[(IV-6) Example 6: Optical Film 6]
The optical film 6 was produced in the same manner as in Example 1 described above, except that the pre-sintering polymer 1 preparation liquid A was changed to the pre-sintering polymer 5 preparation liquid E.

[(IV-7) Example 7: Optical film 7]
The optical film 7 was produced in the same manner as in Example 1 described above, except that the pre-sintering polymer 1 preparation liquid A was changed to the pre-sintering polymer 6 preparation liquid F.

[(IV-8) Example 8: Optical film 8]
The optical film 8 was produced in the same manner as in Example 1 described above, except that the preparation liquid A of the pre-firing polymer 1 was changed to the preparation liquid G of the pre-firing polymer 7.

[(IV-9) Example 9: Optical film 9]
The optical film 8 was produced in the same manner as in Example 1 described above, except that the pre-sintering polymer 1 preparation liquid A was changed to the pre-sintering polymer 8 preparation liquid H.

[(IV-10) Example 10: Optical film 10]
The same procedure as in Example 1 described above except that the amount of the hollow silica particle 1 dispersion liquid was changed to 0.3 ml and the preparation liquid A of the pre-firing polymer 1 was changed to the preparation liquid I of the pre-firing polymer 1. The optical film 10 was manufactured.

[(IV-11) Example 11: Optical film 11]
The optical film is the same as in Example 1 described above, except that the preparation liquid A of the pre-firing polymer 1 is changed to the preparation liquid J of the pre-firing polymer 1 and the liquid amount of the preparation liquid J is changed to 0.1 ml. 11 was manufactured.

[(IV-12) Example 12: Optical film 12]
The optical film 12 was produced in the same manner as in Example 1 described above, except that the preparation liquid A of the pre-firing polymer 1 was changed to the preparation liquid K of the pre-firing polymer 9.

[(IV-13) Example 13: Optical film 13]
The optical film 13 was produced in the same manner as in Example 1 described above, except that the preparation liquid A of the pre-firing polymer 1 was changed to the preparation liquid L of the pre-firing polymer 10.

[(IV-14) Example 14: Optical film 14]
The optical film 14 was produced in the same manner as in Example 1 described above, except that the pre-sintering polymer 1 preparation liquid A was changed to the pre-sintering polymer 11 preparation liquid M.

[(IV-15) Example 15: Optical film 15]
The optical film 15 was produced in the same manner as in Example 1 described above, except that the preparation liquid A of the pre-firing polymer 1 was changed to the preparation liquid N of the pre-firing polymer 12.

[(IV-16) Example 16: Optical film 16]
The optical film 16 was produced in the same manner as in Example 1 described above, except that the preparation liquid A of the pre-firing polymer 1 was changed to the preparation liquid O of the pre-firing polymer 13.

[(IV-17) Example 17: Optical film 17]
The same procedure as in Example 1 described above except that the amount of the hollow silica particle 1 dispersion liquid was changed to 0.25 ml and the preparation liquid A of the pre-firing polymer 1 was changed to the preparation liquid P of the pre-firing polymer 1. The optical film 17 was manufactured.

[(IV-18) Example 18: Optical film 18]
The optical film is the same as in Example 1 described above, except that the preparation liquid A of the pre-firing polymer 1 is changed to the preparation liquid Q of the pre-firing polymer 1 and the liquid volume of the preparation liquid Q is changed to 0.1 ml. 18 was manufactured.

[(IV-19) Example 19: Optical film 19]
The optical film 19 was produced in the same manner as in Example 1 described above, except that the pre-sintering polymer 1 preparation liquid A was changed to the pre-sintering polymer 1 / titanium oxide particle preparation liquid R.

[(IV-20) Example 20: Optical film 20]
The substrate (slide glass water edge polishing material: soda glass square 3 (thickness) × 40 × 40 mm) was ultrasonically cleaned with isopropyl alcohol for 30 minutes and dried. Then, dust was removed by ozone cleaning for 30 minutes and a substrate cleaning spray to obtain a coating glass substrate. 0.42 ml of the hollow silica particle 1 dispersion liquid was spin-coated on this film at a rotation speed of 2685 rpm for 60 seconds using a spin coater. Next, 0.3 ml of the pre-baking polymer 1 preparation solution A was spin-coated at a rotation speed of 2685 rpm for 60 seconds using a spin coating device, and fired at 200 ° C. for 2 hours to produce an optical film 20.

[(IV-21) Example 21: Optical film 21]
The optical film 21 was manufactured in the same manner as in Example 1 described above, except that the hollow silica particle 1 dispersion was changed to the hollow silica particle dispersion 2.

[(IV-22) Example 22: Optical film 22]
The optical film 22 was manufactured in the same manner as in Example 1 described above, except that the hollow silica particle 1 dispersion was changed to the hollow silica particle dispersion 3.

[(IV-23) Comparative Example 1: Optical Film 23]
Substrate (slide glass water edge polishing material: soda glass square 3 (thickness) x 40 x 40 mm) is ultrasonically cleaned with isopropyl alcohol for 30 minutes, dried, then ozone cleaned for 30 minutes, and dust is removed with a spray for substrate cleaning. It was removed and used as a glass substrate for coating. 0.3 ml of the pre-baking polymer 1 preparation solution A was spin-coated on this film at a rotation speed of 2685 rpm for 60 seconds and fired at 200 ° C. for 2 hours to produce an optical film 23. ..

[(IV-24) Comparative Example 2: Optical Film 24]
The substrate (slide glass water edge polishing material: soda glass square 3 (thickness) × 40 × 40 mm) was ultrasonically cleaned with isopropyl alcohol for 30 minutes and dried. Then, dust was removed by ozone cleaning for 30 minutes and a substrate cleaning spray to obtain a coating glass substrate. 0.42 ml of the non-hollow SiO ₂ dispersion liquid was spin-coated on this membrane at a rotation speed of 2685 rpm for 60 seconds using a spin coater. Next, 0.3 ml of the pre-baking polymer 1 preparation solution A was spin-coated at a rotation speed of 2685 rpm for 60 seconds using a spin coating device, and fired at 200 ° C. for 2 hours to produce an optical film 24.

[(IV-25) Comparative Example 3: Optical Film 25]
The optical film 25 was produced in the same manner as in Example 1 described above, except that the preparation liquid A of the pre-firing polymer 1 was changed to the polysiloxane preparation liquid S.

[(IV-26) Comparative Example 4: Optical Film 26]
Substrate (slide glass water edge polishing material: soda glass square 3 (thickness) x 40 x 40 mm) is ultrasonically cleaned with isopropyl alcohol for 30 minutes, dried, then ozone cleaned for 30 minutes, and dust is removed with a spray for substrate cleaning. It was removed and used as a glass substrate for coating. 0.42 ml of the hollow silica particle dispersion liquid 1 was spin-coated on this film at a rotation speed of 2685 rpm for 60 seconds using a spin coating device, and fired at 200 ° C. for 2 hours to produce an optical film 26. ..

[(IV-27) Comparative Example 5: Optical Film 27]
The optical film 27 was manufactured in the same manner as in Example 1 described above, except that the hollow silica particle dispersion liquid 1 was changed to the hollow silica particle dispersion liquid 4.

[(IV-28) Comparative Example 6: Optical Film 28]
The optical film 28 was manufactured in the same manner as in Example 1 described above, except that the hollow silica particle dispersion liquid 1 was changed to the hollow silica particle dispersion liquid 5.

Tables 1 and 2 below show the configurations and refractive indexes of the optical films 1 to 28.

[Refractive index measurement]
The refractive index of the optical film was measured using an automatic multi-incident angle spectroscopic ellipsometer V-VASE (manufactured by JA Woolam). The measurement condition was 23 ° C., and the refractive index with a wavelength of 589 nm was read. The results are shown in Table 1.

* 1: The intermediate layer is located between the substrate (slide glass) and the optical film.

In Examples 4 and 20 and Comparative Examples 1, 2 and 4, the intermediate layer was not formed.
* 2: Based on the number of moles of all metal atoms (Ti + Si) in the composite polymetallosane, the content of titanium atoms in the polytitanoxane moiety is a ¹ (mol%), and the titanium atom in the polytitanosiloxane moiety. The content is a ² (mol%).
* 3: "Hollow particles" in the low refractive index material in the table are hollow silica particles [see (I-1), (I-4) to (I-7) above], and "porous MgF2" is porous. MgF ₂ particles [see (I-2) above] and “SiO2” refer to non-hollow SiO ₂ particles [see (I-3) above].

* 1: The intermediate layer is located between the substrate (slide glass) and the optical film.
* 2: Based on the total weight of the optical film, the content weight% of the low refractive index material is b (% by weight), and the content weight% of the composite polymetalloxane fired film or polysiloxane fired film is c (weight%). ..
* 3: Based on the total weight of the optical film, the content weight% of the low refractive index material is b (% by weight), the content weight% of the composite polymetalloxane fired film or the polysiloxane fired film is c (weight%), and oxidation. Let d (% by weight) be the content weight% of the titanium particles.
* 4: The absorption intensity derived from Ti-O-Ti is defined as A ¹ and the absorption intensity derived from Ti-O-Si is defined as A ² by quantitative analysis of the composite polymetalloxane fired film by infrared spectroscopy.
* 5: “Hollow particles” in the low refractive index materials in the table are hollow silica particles [see (I-1), (I-4) to (I-7) above], and “porous MgF2” is porous. MgF ₂ particles [see (I-2) above] and “SiO2” refer to non-hollow SiO ₂ particles [see (I-3) above].

[(V) Performance evaluation]
[(V-1) Antifouling property evaluation]
The optical film was irradiated with a UV irradiator (Ushio, Inc. multi-light basic configuration unit ML-251A / B, irradiation optical unit PM25C-100) for 60 minutes. Next, 1 ml of oil (canola oil) was poured onto the optical film and left at room temperature for 15 minutes. Then, it was rinsed with 50 ml of tap water. The optical film after running water was visually observed, and the antifouling property of the optical film was evaluated according to the evaluation criteria shown below. The results are shown in Table 3.
◯: Almost all the oil has run off (95% or more removed).
Δ: A very small amount of oil remains (90 to 95% removed).
Δ ×: Part of the oil remains (60 to less than 90% removed).
X: Most of the oil remains (less than 60% removed).

[(V-2) Antireflection evaluation]
Using a reflection spectroscopic film thickness meter (FE3000 manufactured by Otsuka Electronics Co., Ltd.), measure the reflectance of the optical film at a wavelength of 350 nm to 550 nm at an incident angle of 0 degrees, and prevent the reflection of the optical film according to the evaluation criteria shown below. Gender was evaluated. The results are also shown in Table 3.
⊚: The maximum reflectance is less than 1%, and the range (maximum reflectance-minimum reflectance) is 0.5% or less.
◯: The maximum reflectance is less than 1%, and the range (maximum reflectance value-minimum reflectance value) exceeds 0.5% and is 1% or less.
Δ: The maximum reflectance is 1% or more and less than 2%.
Δ ×: The maximum reflectance is 2% or more and less than 4%.
X: The maximum reflectance is 4% or more.

[(V-3) Transparency evaluation]
The optical film was measured using a spectrophotometer UV-Vis (U-3310 manufactured by Hitachi High-Tech Science Co., Ltd.) at an incident angle of 0 degrees and the transmittance of wavelengths from 350 nm to 550 nm was measured, and the optical film was measured according to the evaluation criteria shown below. Transparency was evaluated. The results are also shown in Table 3.
⊚: The minimum transmittance is 98% or more.
◯: The minimum transmittance is 96% or more and less than 98%.
Δ: The minimum transmittance is 94% or more and less than 96%.
Δ ×: The minimum transmittance is 92% or more and less than 94%.
X: The minimum transmittance is less than 92%.

[(V-4) Scratch resistance evaluation]
The surface hardness was measured by a pencil hardness test according to JIS K5400. The results are shown in Table 3.

◯: Hardness H or higher Δ: Hardness F, HB, B
×: Hardness 2B or less

* 1: Hollow silica particles could not form a layer because there was no material that could function as a binder.

As is clear from the evaluation results shown in Table 3, the optical film of the present invention was able to obtain an optical film having excellent antireflection and antifouling properties without significantly reducing the transparency.

A more detailed explanation is as follows.

(I)
By comparing Example 20 with Comparative Example 1 in which the low refractive index material is not used at all, it can be seen that both the antireflection property and the transparency are improved due to the presence of the low refractive index material.

(Ii)
Comparative Example 2 roughly corresponds to an example in which the hollow silica particles 1 <refractive index 1.30) of Example 20 _{are replaced with non-hollow SiO 2 particles <refractive index 1.46).} Example 20 using hollow silica particles 1 <refractive index 1.2) has significantly higher antireflection and transparency than Comparative Example 2 using _{non-hollow SiO 2 particles <refractive index 1.46).} Show that it is excellent.

(Iii)
Comparative Example 3 roughly corresponds to an example in which the composite polymetalloxane fired film in the optical film of Example 1 is replaced with a simple polysiloxane fired film. Example 1, which is considered to have a polytitanoxane moiety that acts as an antifouling material, shows that the antifouling property is significantly superior to that of Comparative Example 3 without it.

(Iv)
Comparative Example 4 roughly corresponds to the example of Example 20 lacking the composite polymetallosane fired film (and therefore lacking the antifouling layer). In Comparative Example 4, since the hollow silica particles could not form a layer, it is shown that the composite polymetalloxane also serves as a binder for forming an optical film.

(V)
Comparative Example 5 roughly corresponds to an example in which the hollow silica particles 1 <refractive index 1.30) of Example 1 are replaced with hollow silica particles 4 (refractive index 1.21) having a lower refractive index. Since the low refractive index material of Comparative Example 5 has a lower refractive index, it is of course superior in terms of antireflection and transparency, but in terms of scratch resistance, the result of Example 1 is superior. rice field.

(Vi)
Comparative Example 6 roughly corresponds to an example in which the hollow silica particles 1 <refractive index 1.30) of Example 1 are replaced with hollow silica particles 5 (refractive index 1.33) having a higher refractive index. In Example 1, since a low refractive index material having a lower refractive index was used, both antireflection and transparency were superior to those of Comparative Example 6.

(Vii)
^{In Examples 8 and 15, the titanium atom content ratio (a 1} / a ² ) between the polytitanoxane moiety and the polytitanosiloxane moiety in the composite polymetallosane fired film is set to be relatively large. .. On the other hand, in Examples 6, 7, 12, 14, 16 and the like, on the contrary, this is set to be relatively small. Since the former tended to have higher antifouling property, it is considered that the polytitanoxane moiety in the polycondensation polymer has a greater effect on the antifouling property.

Further, in these examples, the ratio of ^{the infrared absorption intensity A 1} derived from Ti-O-Ti and the infrared absorption intensity A 1 derived from Ti-O-Si ^{in the composite polymetalloxane fired film to A 2 is A 1} /. A ² shows almost the same value as a ¹ / a ^2. It is considered that the polytitanoxane moiety Ti—O—Ti bond and the polytitanosiloxane moiety reflect the Ti—O—Si bond.

(Viii)
In Example 12, the antifouling property evaluation was lower than in the other examples, which means that the A ¹ / A ² ratio or the a ¹ / a ² ratio was lower than in the other examples, that is, , Ti—O—Ti bond or polytitanoxane moiety is considered to indicate that the antifouling property is affected.

The optical film of the present invention is excellent in transparency, antireflection, and antifouling property (self-cleaning), and can be applied to optical panels such as solar panels and displays, and optical lenses such as surveillance cameras. In particular, when applied to solar panels, power generation efficiency can be improved.

Claims (17)

A composite poly comprising (A) a low refractive index material exhibiting a refractive index of 1.22 to 1.32, and (B) a polycondensation structure of a metal alkoxide containing at least one or more alkoxysilanes and one or more alkoxytitaniums. Metalloxane,
It is an optical film containing
The alkoxysilane of the composite polymetalloxane contains at least one or more organic groups selected from the group of cationically polymerizable organic groups, saturated or unsaturated hydrocarbon groups having 1 to 21 carbon atoms, and substituted or unsubstituted aryl groups. Have and
An optical film characterized in that the polycondensation structure contains at least a Ti—O—Ti bond and a Si—O—Ti bond. (A) A low refractive index material exhibiting a refractive index of 1.22 to 1.32, and
(B) A composite polymetalloxane containing a polycondensation structure of one or more metal alkoxides selected from the group consisting of alkoxysilanes and alkoxytitaniums.
It is an optical film containing
The polycondensation structure contains at least a Ti—O—Ti bond and a Si—O—Ti bond.
The optical Gakumaku you, wherein the low refractive index material is a hollow particle. (A) A low refractive index material exhibiting a refractive index of 1.22 to 1.32, and
(B) A composite polymetalloxane containing a polycondensation structure of one or more metal alkoxides selected from the group consisting of alkoxysilanes and alkoxytitaniums.
It is an optical film containing
The alkoxysilane of the composite polymetalloxane contains at least one or more organic groups selected from the group of cationically polymerizable organic groups, saturated or unsaturated hydrocarbon groups having 1 to 21 carbon atoms, and substituted or unsubstituted aryl groups. Have and
The polycondensation structure contains at least a Ti—O—Ti bond and a Si—O—Ti bond.
The composite polymetalloxane contains polytitanoxane having a polycondensation structure of alkoxytitanium and polytitanosiloxane having a polycondensation structure of alkoxysilane and alkoxytitanium, and the polytitanoxane and the polytitanosiloxane are contained. light Gakumaku you wherein a is obtained by condensation bound at least in part. The content a1 (mol%) of the alkoxytitanium unit a contained in the polytitanoxane and the content a2 (mol%) of the alkoxytitanium unit a contained in the polytitanosiloxane are expressed by the following formulas (viii), (viii). The optical film according to claim 3, wherein the relationship of ix) and (x) is satisfied.
2 ≤ a1 / a2 (viii)
6.25 ≤ a1 ≤ 53 (ix)
0.50 ≤ a2 ≤ 6.25 (x) Wherein the content b of the low refractive index material, the composite polymetalloxane content c is the optical film according to claim 3 or 4, characterized in that satisfies the following formula (xii).
0.18 ≦ b / c ≦ 61 (xii) By quantitative analysis of infrared spectroscopy, the absorption intensity of the absorption band 840 cm-1 derived from the Ti—O—Ti bond is A1, and the absorption intensity of the absorption band 950 cm-1 derived from the Si—O—Ti bond. The optical film according to any one of claims 1 to 5, wherein the optical film satisfies the relationship of the following formula (xi) when A2 is used.
2 ≤ A1 / A2 (xi) (A) A low refractive index material exhibiting a refractive index of 1.22 to 1.32, and
(B) A composite polymetalloxane containing a polycondensation structure of one or more metal alkoxides selected from the group consisting of alkoxysilanes and alkoxytitaniums.
It is an optical film containing
The polycondensation structure contains at least a Ti—O—Ti bond and a Si—O—Ti bond.
Light Gakumaku characterized by further containing titanium oxide particles. The optical film further contains titanium oxide particles, and the content b of the low refractive index material, the content c of the composite polymetalloxane , and the content d of the titanium oxide particles satisfy the following formula (xiii). The optical film according to any one of claims 3 to 5, wherein the optical film is characterized by this.
d / (b + c + d) ≤ 0.1 (xiii) The optical film according to any one of claims 1 to 6, further comprising titanium oxide particles. The alkoxysilane of the composite polymetalloxane contains at least one or more organic groups selected from the group of cationically polymerizable organic groups, saturated or unsaturated hydrocarbon groups having 1 to 21 carbon atoms, and substituted or unsubstituted aryl groups. The optical film according to any one of claims 2 to 5, 7, and 8, characterized in that it has. The optical film according to any one of claims 2 to 10, wherein the composite polymetalloxane contains one or more kinds of alkoxy titanium and one or more kinds of alkoxysilane. The optical film according to any one of claims 1, 3, 5, 7, and 8, wherein the low refractive index material is hollow particles. A base material comprising a transparent base material and the optical film according to any one of claims 1 to 12 provided on the transparent base material . An optical device having a base material and an optical film provided on the base material.
The optical film is
(A) A low refractive index material exhibiting a refractive index of 1.22 to 1.32, and
(B) A composite polymetalloxane containing a polycondensation structure of one or more metal alkoxides selected from the group consisting of alkoxysilanes and alkoxytitaniums.
Including
The polycondensation structure contains at least a Ti—O—Ti bond and a Si—O—Ti bond.
Further comprising an intermediate layer, an optical device, characterized in that said intermediate layer comprises a low refractive index material of the non-hollow particles between the optical film and the substrate. The optical device according to claim 14, wherein the low refractive index material exhibiting a refractive index of 1.22 to 1.32 is hollow particles. An optical device having a transparent base material and the optical film according to any one of claims 1 to 12 provided on the transparent base material. The optical device according to any one of claims 14 to 16, wherein the optical device is a solar panel, a display device, or an optical lens.