JP2000334881A - Cage-shaped silsesquioxane-containing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cage-shaped silsesquioxane-containing film suitable for a reflection preventing film good in optical characteristics by coating a base material with a composite compsn. prepared by mixing cage-shaped silsesquioxane with an org. or inorg. polymer. SOLUTION: An org. polymer may be used independently or may be used as a combination of two or more kinds of org. polymers or may be used together with a low.mol. wt. org. compd. Any one of metal, glass, silicon and a resin may be used as a base material but a transparent base material is pref. By adding cage-shaped silsesquioxane, fine gaps can be simply formed in a film and, as a result, the refractive index of the film lowers and the dielectric constant among physical properties of the film also lowers. That is, by coating the base material with cage-shaped silsesquioxane by a binder, a film low in refractive index and dielectric constant can be formed and a film improved in optical characteristics like a reflection preventing film can be formed and the strength or durability of the film is also improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a metal oxide sol composition, a metal oxide gel composition, a resin composition and a metal oxide sol composition having fine voids, characterized by containing cage silsesquioxane. The present invention relates to a cage-like silsesquioxane-containing film formed by the method and a method for producing the same, and further relates to an optical property improving film having the film.

[0002]

2. Description of the Related Art In recent years, research and development of functional thin films such as optical functional materials, electronic functional materials, and chemical biological functional materials have been actively conducted. Among functional thin films, research and development of functional materials using metal oxide-containing coatings and organic resin coatings have been actively conducted.Specifically, solar cells, transparent electrodes, optical memories, battery electrolytes, catalysts, etc. Research and development have been reported. The “metal” mentioned here also includes silicon and boron which are usually defined as “non-metal” in the periodic table.

In recent years, a large number of electronic displays typified by liquid crystal displays and plasma display panels have been developed and put to practical use. With the development of these displays, optical property improving films for the purpose of beauty, legibility, reduction of the influence of the human body, prevention of malfunction, and the like have been widely studied and actually used. Typical examples of such a film include an anti-glare film, an anti-reflection film (anti-reflection film), a viewing angle widening film, a light control film, an electromagnetic wave shielding film, an infrared (heat ray) cut film, and the like. A metal oxide-containing film or an organic resin film can also be used for the improved film.

For example, in the case of an anti-reflection film, _three to four layers of metal oxide films having different refractive indexes such as SiO ₂ , TiO ₂ , ZrO ₂ , Y ₂ O ₃ and organic polymer films are usually laminated. It is made.

According to an optical simulation, if a single-layer film having a refractive index of 1.25 or less can be formed at the time of manufacturing an antireflection film, it is not necessary to adopt a multilayer structure as described above. However, a technique for obtaining a film having such an ultra-low refractive index and excellent film properties has not been developed at present, and its development is desired.

[0006] In addition to the optical film, for example, IC
In semiconductors such as semiconductors and LSIs, a material having a lower dielectric constant (Low K material) is required, and a metal oxide such as SiO ₂ is used as the material, but the refractive index is basically low. It is known that a material has a tendency to have a lower dielectric constant, and from this viewpoint, a similar material (a material having a low dielectric constant, that is, a material having a low refractive index) is required.

On the other hand, as a method of obtaining a metal oxide thin film, homogeneity, transparency, wide selection of materials, etc.
The sol-gel method using a metal alkoxide and its hydrolyzate is widely used.

In recent years, an organic / inorganic hybrid film in which an inorganic polymer and an organic polymer are homogenized by further using an organic compound to further impart a function or improve physical properties has been studied. .

[0009]

With respect to the improvement of the optical characteristics, a technique for producing an ultra-low refractive index film having good film strength and durability, which constitutes an antireflection film, is desired. A technique for encapsulating air or gaseous molecules in a film with a size on the order of nanometers is required, and a technique for producing such fine voids uniformly over a large area at low cost has not been found at all. The present invention solves the above problems, and specifically provides a novel cage-like silsesquioxane-containing coating and a method for producing the same.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have developed a composite composition in which a cage silsesquioxane having a porosity in the order of angstroms in a molecule itself is mixed with an organic polymer or an inorganic polymer (metal oxide gel). The present inventors have found that a film containing microscopic voids can be easily obtained by applying an object on a substrate, and the present invention has been accomplished.

The present invention has been achieved by the following constitutions.

1. A film comprising a transparent substrate and a film containing at least one kind of cage silsesquioxane.

2. 2. The film according to the above 1, wherein the cage-like silsesquioxane is a compound represented by the following general formulas (1) to (7).

[0014]

Embedded image

[0015]

Embedded image

(In the formula, R represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and a plurality of Rs may be the same.) A composition characterized by being a metal oxide sol or a metal oxide gel in which at least one metal alkoxide or metal salt contains at least one cage silsesquioxane.

4. Formed by applying a metal oxide sol or a metal oxide gel composition containing at least one kind of cage silsesquioxane to at least one kind of metal alkoxide or metal salt on a substrate A cage-like silsesquioxane-containing coating characterized by the following.

5. A cage comprising applying a metal oxide sol or a metal oxide gel composition containing at least one kind of cage silsesquioxane to at least one kind of metal alkoxide or metal salt on a substrate. A method for producing a silsesquioxane-containing film.

6. A resin composition characterized in that at least one kind of organic polymer contains at least one kind of cage silsesquioxane.

[7] FIG. A cage-like silsesquioxane-containing resin composition formed by applying a resin composition containing at least one kind of cage-like silsesquioxane to at least one kind of organic polymer on a substrate. Film.

8. A method for producing a cage-like silsesquioxane-containing film, comprising applying a resin composition containing at least one kind of cage-like silsesquioxane to at least one kind of organic polymer on a substrate.

9. A film containing cage silsesquioxane is a metal oxide sol or metal oxide gel composition containing at least one cage silsesquioxane in at least one metal alkoxide or metal salt,
3. The film according to the above item 1 or 2, wherein the film is formed by coating on a transparent substrate.

10. A film containing cage silsesquioxane was formed by applying a resin composition containing at least one kind of cage silsesquioxane to at least one kind of organic polymer on a transparent substrate. 3. The film according to the above 1 or 2, which is a film.

11. A film containing cage silsesquioxane is coated with at least one metal alkoxide or metal salt and at least one organic polymer with at least one metal alkoxide or metal salt.
A polymer composite metal oxide sol or a polymer composite metal oxide gel composition containing a kind of cage silsesquioxane, which is formed by coating on a transparent substrate. 2, 9, or 10
The film according to 1.

Hereinafter, the present invention will be described in detail.

Therefore, by using the cage silsesquioxane of the present invention, a metal oxide film obtained from a metal alkoxide or a metal salt, a metal oxide film obtained from a sol or gel compound, or a metal oxide film obtained from the metal oxide film or an organic compound, A film having voids on the order of angstroms can be easily obtained from a so-called inorganic-organic composite film or an organic polymer film. In the film containing the cage-like silsesquioxane of the present invention, the cage-like silsesquioxane has molecular-level vacancies. can do. In other words, in the present invention, a low-refractive-index, low-dielectric-constant film can be produced by adding a cage-like silsesquioxane to some kind of binder and coating it on a substrate, thereby improving optical properties such as an antireflection film. It was found that a film could be produced.

The cage silsesquioxane used in the present invention will be described.

Silsesquioxane (Silsesquioxane)
oxane) is also called T resin, and ordinary silica is represented by the general formula of [SiO ₂ ], whereas silsesquioxane (also called polysilsesquioxane) is represented by [RSiO _1.5 ]. A compound in which one alkoxy group of tetraalkoxysilane (Si (OR ′) ₄ ) typically represented by tetraethoxysilane is replaced with an alkyl group or an aryl group (RSi (O
R ') ₃ ) A polysiloxane synthesized by hydrolysis-polycondensation of a compound, and typically has an amorphous, ladder-like, or cage-like (completely condensed cage-like) molecular arrangement.

The cage silsesquioxane used in the present invention is, specifically, a type represented by the chemical formula [RSiO _1.5 ] ₈ (general formula (1)), [RSiO _1.5 ] ₁₀
(General formula (2)) represented by the chemical formula
O _1.5 ] ₁₂ (general formula (3)), [RSiO _1.5 ] ₁₄ type (general formula (4), general formula (5)) and [RSiO
_1.5 ] The types (general formulas (6) and (7)) represented by ₁₆ chemical formulas are known.

Among them, the most preferable one for use in the present invention is one having a cubic structure represented by the general formula (1) (also called T8-silsesquioxane).

More specifically, “Journal of the Society of Polymer Science, No. 47
Vol. December issue (1998), page 899 ”and the catalog“ Special Silicon Reagent, 7th Edition (issued on November 3, 1998) ”issued by Chisso Corporation / Azmax Corporation. Have been.

In the compounds represented by formulas (1) to (7) of the present invention, the alkyl group represented by R may be linear or branched, and further substituted by a substituent. It may be. Specifically, methyl, ethyl, cyclopentyl, cyclohexyl, isopropyl, 2-ethylhexyl, tert-butyl, 2-chloroethyl, methacryloxypropyl,
Examples include an allyl group, a 3-aminopropyl group, a 3-mercaptopropyl group, and a 3-glycidoxypropyl group.

In the compounds represented by the general formulas (1) to (7) of the present invention, the alkenyl group represented by R is
It may be linear or branched, and may be further substituted by a substituent. Specifically, a vinyl group,
Examples thereof include a 1-cyclohexenyl group and a 2,2-dimethylvinyl group.

In the compounds represented by formulas (1) to (7) of the present invention, the aryl group represented by R is 6
It may be a π system or a 10π system, and may be further substituted with a substituent. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a phenanthryl group.

In the compounds represented by the general formulas (1) to (7) of the present invention, among the substituents represented by R or a hydrogen atom, preferred are a hydrogen atom, a methyl group, an ethyl group and a cyclopentyl group. , Cyclohexyl group, isopropyl group,
2-ethylhexyl group, 2-chloroethyl group, methacryloxypropyl group, allyl group, 3-aminopropyl group,
3-mercaptopropyl group, 3-glycidopropyl group,
A vinyl group and a phenyl group.

R ′ represents the same alkyl group as a preferable substituent of R.

The cage silsesquioxane is synthesized by hydrolysis-polycondensation of the corresponding (RSi (OR ') ₃ ) compound, and specific examples thereof are shown below.

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

Among them, hydro-T8-silsesquioxane (S-1), methacryloxypropylheptacyclopentyl-T8-silsesquioxane (S-12), octakis (dimethylsiloxy) -T8-silsesquioxane Sun (S-13) and octavinyl-T8-silsesquioxane (S-14) are commercially available from Chisso Corporation.

The “metal” of the metal alkoxide and metal salt used in the present invention generally includes “transition metal (Tr)” in addition to “metals” defined in the periodic table and the like.
anion metals) "
All elements of "lanthanoid", all elements of "actinoid", and "Non Metals"
Is defined as containing boron and silicon (silicon).

To obtain a metal oxide film from a metal alkoxide, a method called a so-called sol-gel method is used. That is, in order to enable a sol-gel reaction at a low temperature to the metal alkoxide solution, preferably, an acid catalyst is added to cause a hydrolysis to accelerate the condensation reaction to produce a metal oxide film sol or gel. This is applied to a substrate and dried, and then, if necessary, a heat treatment, an ultraviolet treatment, a plasma treatment, or the like is performed to obtain a metal oxide film with advanced three-dimensional crosslinking. Here, as the catalyst, generally used are inorganic acids such as hydrochloric acid, acetic acid and nitric acid, and organic acids such as acetic acid, trifluoroacetic acid, p-toluenesulfonic acid and methanesulfonic acid. In addition, Lewis acids, for example, acetates of metals such as germanium, titanium, aluminum, antimony, and tin, other organic acid salts, halides, and phosphates may be used in combination.

As a catalyst, DBU (diazabicycloundecene-1), DBU such as monoethanolamine, diethanolamine, triethanolamine, diethylamine and triethylamine may be used instead of such acids.
Bases such as bicyclocyclic amines such as N (diazabicyclononene), ammonia, and phosphine can be used. Furthermore, acid and base treatments may be used multiple times.

The components such as metal alkoxides are dissolved or dispersed in a solvent. As the solvent, the above-mentioned metal alkoxides, and if necessary, an organic compound, a catalyst, etc., for example, on a plastic film, a glass substrate, etc. Painted,
When forming a thin film, it is necessary to evaporate the solvent after coating, so a volatile solvent is preferable, and it does not react with metal alkoxides, organic compounds, catalysts, etc., and does not dissolve a substrate such as a plastic film. Any solvent can be used as long as the solvent is usually used. For example, ethyl alcohol, methyl alcohol, isopropyl alcohol, n-propyl alcohol, alcohols such as methoxymethyl alcohol, water, ethyl acetate, acetate such as methyl acetate,
Examples thereof include ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, ethylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, dimethylformamide, dimethyl sulfoxide, and acetylacetone.

By incorporating the silsesquioxane of the present invention into a metal oxide film obtained from a metal alkoxide or a metal salt by the above method, a metal oxide film having fine pores can be obtained.

In the metal alkoxide used in the present invention, examples of the alkoxide of Al include aluminum (III) n-butoxide, aluminum (III) s-butoxide, aluminum (III) t-butoxide,
Aluminum (III) ethoxide, aluminum (II
I) isopropoxide, aluminum (III) s-butoxide bis (ethyl acetoacetate), aluminum (III) di-s-butoxide ethyl acetoacetate, aluminum (III) diisopropoxide ethyl acetoacetate, aluminum (III) Ethoxy ethoxy ethoxide, aluminum hexafluoropentadionate, aluminum (III) 3-hydroxy-2-
Methyl-4-pyronate, aluminum 9-octadecenylacetoacetate diisopropoxide, aluminum (III) 2,4-pentanedionate, aluminum phenoxide, aluminum (III) 2,2,6
6, -tetramethyl-3,5-heptanedionate, S
Examples of the alkoxide of i include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, methyl Trimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, Examples of trimethylbutoxysilane and alkoxide of Ti include titanium n-butoxide, titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium Sopuropokisaido, titanium t-
Butoxide, titanium n-nonyl oxide, titanium i
-Butoxide, titanium methoxypropoxide, titanium chlorotriisopropoxide, titanium dichloride diethoxide, titanium iodoisopropoxide, titanium di-n-butoxide (bis-2,4-pentadionate), titanium dii-propoxide (bis -2,4-pentadionate), titanium diisopropoxide bis (tetramethylheptane dionate), titanium diisopropoxide bis (ethyl acetoacetate), titanium 2-ethylhexoxide, titanium oxide bis (pentadioxide Nitrate), titanium oxybis (tetramethyl heptane dionate), tetrakis (trimethylsiloxy)
Titanium, titanium allyl acetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium methacrylate triisopropoxide, (2-methacryloxyethoxy) triisopropoxy titanate, titanium methacryloxyethyl acetoacetate triisopropoxide Examples of the side, titanium methylphenoxide, and alkoxide of V include vanadium triisopropoxide oxide, vanadium triisobutoxide oxide, and vanadium (III) 2,4
Examples of pentanedionate, vanadium (IV) oxide bis (2,4-pentanedionate), vanadium (IV) oxybis (benzoylacetonate), and alkoxide of Zn include zinc N, N-dimethylamino ethoxide, zinc Examples of methoxy ethoxide, zinc 2,4-pentanedionate, zinc-2,2,6,6-tetramethyl 3,5-heptanedionate, and alkoxide of Sr include strontium isopropylate and strontium methoxyoxide. , Strontium hexafluoropentanedionate, strontium 2,4-pentanedionate, strontium 2,2,6,6,-
Examples of tetramethyl-3,5-heptanedionate, alkoxide of Y include yttrium isopropoxide, yttrium methoxy ethoxide, yttrium hexafluoropentanedionate, yttrium 2,
4-pentanedionate, yttrium hexafluoroisopropoxide diammonium complex, yttrium 6,6,7,7,8,8,8-heptafluoro-2,2
-Dimethyl-3,5-octane dionate, yttrium 2,2,6,6-tetramethyl-3,5-heptanedionate, examples of alkoxides of Zr include zirconium ethoxide, zirconium isopropoxide,
Zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium 2-ethylhexyl oxide, zirconium 2-
Methyl-2-butoxide, tetrakis (trimethylsiloxy) zirconium, zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium diisopropoxide bis (2,2,6,6, -tetramethyl-3) , 5-heptanedionate, zirconium dimethacrylate dibutoxide, zirconium hexafluoropentanedionate, zirconium methacryloxyethyl acetoacetate tri-n-propoxide, zirconium 2,4-pentanedionate, zirconium 2,2,6,6- Examples of tetramethyl-3,5-heptanedionate, zirconium trifluoropentanedionate, and alkoxides of In include indium methoxy ethoxide, indium isopropoxide, and indium n-propyl. Pokisaido, indium n- butoxide, indium t- butoxide, indium hexafluoropentanedionate, indium 2,4
Examples of pentanedionate, indium methyl (trimethyl) acetylacetonate, indium trifluoropentanedionate, Sn alkoxide include:
Tin (II) methoxide, tin (II) ethoxide, tetraisopropoxy tin, tetra-t-butoxy tin,
Examples of tetra-n-butoxy tin, bis (2,4-pentanedionate) dicross, tin (II) 2,4-pentanedionate, sodium tin ethoxide, and alkoxide of Ta include tantalum (IV) methoxide and tantalum. (IV) ethoxide, tantalum (IV) isopropoxide, tantalum (IV) n-propoxide, tantalum (IV) n-butoxide, tantalum (IV) t-butoxide, tantalum sodium methoxide, tantalum (IV) trifluoroethoxide , Tantalum (IV) tetraethoxide pentanedionate, examples of alkoxides of W include tungsten (V) ethoxide, tungsten (VI) ethoxide, tungsten (VI) phenoxide, and alkoxides of Tl include thallium (I) ) Ethoxide, Tali (I) isopropoxide, thallium (I) n-propoxide, thallium (I)
Examples of alkoxides of n-butoxide, thallium (I) t-butoxide, thallium (I) thallium 2,4-pentadionate, and Sb include antimony (III) methoxide, antimony (III) ethoxide, and antimony (III) n -Butoxide, antimony (III) t-butoxide, and alkoxides of Ce include cerium (IV) ethoxide, cerium (IV) isopropoxide, cerium (IV) n-propoxide, cerium (I
V) n-butoxide, cerium (IV) t-butoxide, cerium (IV) methoxy ethoxide, cerium (III) 2,4-pentadionate, cerium (IV)
2,2,6,6-tetramethylheptanedionate, cerium (III) 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octandionate, cerium (IV) tenoyl trifluoroacetate,
Examples of Li alkoxides include lithium methoxide, lithium ethoxide, lithium isopoloxide, lithium t-butoxide, lithium 2,4-pentanedionate, lithium tetramethylheptanedionate, and Be alkoxides. Examples of alkoxides of beryllium 2,4-pentanedionate B include boron methoxide, boron ethoxide, boron isopropoxide, boron n-butoxide, boron t-butoxide, boron allyl oxide, and examples of alkoxides of Na. Examples of sodium 2,4-pentanedionate, sodium acetylacetonate, sodium aluminum hydride bis (methoxy ethoxide), sodium ethoxide, and Mg alkoxide include: Neshi um methoxide, magnesium ethoxide, magnesium n- propoxide,
Magnesium isopropoxide, magnesium n-butoxide, magnesium t-butoxide, magnesium trifluoropentadionate, magnesium 2,4
Examples of pentadionate, magnesium hexafluoropentadionate, magnesium methoxy ethoxide, magnesium methyl carbonate, and alkoxide of K include potassium t-butoxide, potassium 2,4
Examples of pentanedionate, alkoxide of Ca include calcium methoxide, calcium ethoxide, calcium methoxy ethoxide, calcium 2,
4-pentanedionate, calcium 2,2,6,6-
Tetramethyl-3,5-heptanedionate, calcium hexafluoropentadionate, calcium 6,
Examples of 6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octandionate and alkoxides of Sc include scandium (III) 2,2,6
6-tetramethyl-3,5-heptanedionate, Cr
Examples of the alkoxide of chromium (III) isopropoxide, chromium (III) 2,4-pentanedionate, chromium (III) hexafluoropentanedionate, chromium (III) trifluoropentanedionate,
Chromium (III) benzoylacetonate, chromium (III)
2,2,6,6-tetramethylheptanedionate,
Examples of alkoxides of Co include cobalt carbonyl methoxide and cobalt (III) 2,4-pentanedionate. Examples of alkoxides of Mn include manganese (II) methoxide and manganese (II) 2,4-pentanedionate. Examples of the alkoxides of Fe and Fe include iron (II
I) ethoxide, iron (III) 2,4-pentanedionate, iron (III) trifluoropentanedionate, iron (I
II) Examples of benzoylacetonate and alkoxide of Ni include nickel (II) 2,4-pentanedionate, nickel (II) hexafluoropentanedionate, nickel (II) 2,2,6,6-tetramethyl −
Examples of 3,5-heptanedionate and Cu alkoxide include copper (II) methoxide, copper (II) ethoxide, copper (II) methoxyethoxy ethoxide, and copper (II)
2,4-pentanedionate, copper (II) 2,2,6
6,6-tetramethyl-3,5-heptanedionate,
Copper (II) trifluoropentanedionate, Copper (II) hexafluoropentanedionate, Copper (I) hexafluoropentanedionate cyclooctanediene complex, Copper (II) ethyl acetoacetate, Copper (II) dimethylamino ethoxide , Copper (II) benzoylacetonate, copper (II) 1,3-diphenyl-1,3-propanedionate, copper (II) 6,6,7,7,8,8,8-heptafluoro-2, Examples of alkoxides of 2-dimethyl-3,5-octandionate Ga include gallium (III) ethoxide, gallium (III) 2,4-pentanedionate, and gallium (III) 2,2,6,6,-. Examples of tetramethylheptane dionate and Ge alkoxide include germanium methoxide, germanium ethoxide, germanium isopro Kisaido, germanium n- butoxide, germanium t- butoxide, R
Examples of the alkoxide of b include rubidium 2,4-pentanedionate; examples of the alkoxide of Nb include:
Examples of niobium (V) ethoxide, niobium (V) isopropoxide, niobium (V) n-propoxide, niobium (V) n-butoxide, and alkoxides of Mo include molybdenum (V) ethoxide, molybdenum (V) isopropoxide. Examples of alkoxides of side, molybdenum (V) n-propoxide, molybdenum (V) n-butoxide, molybdenum (VI) oxide bis (2,4-pentanedionate) and Cd include cadmium 2,4-pentanedionate; Examples of alkoxides of Cs include cesium methoxide, cesium ethoxide, cesium isopropoxide, cesium n-propoxide, cesium n-butoxide, cesium t-butoxide, and examples of alkoxides of Ba include barium isopropoxide, ba Um methoxy propoxide, barium n- butoxide, barium t- butoxide, barium 2,4-pentanedionate, barium hexafluoropentanedionate, barium (II)
6,6,7,7,8,8,8-heptanefluoro-2,
Examples of 2-dimethyl-3,5-octandionate, barium (II) 2,2,6,6-tetramethyl-3,5-heptanedionate and alkoxides of La include lanthanum isopropoxide and lanthanum methoxy. Examples of propoxide, lanthanum n-butoxide, lanthanum t-butoxide, lanthanum 2,4-pentanedionate, lanthanum 2,2,6,6-tetramethyl-3,5-heptanedionate, alkoxides of Hf Hafnium ethoxide, hafnium isopropoxide, hafnium methoxypropoxide, hafnium n-butoxide, hafnium t-butoxide, hafnium 2,
Examples of 4-pentanedionate, hafnium tetramethylheptanedionate, hafnium trifluoropentanedionate, and alkoxide of Pb include lead (II).
6,6,7,7,8,8,8-heptafluoro-2,2
-Dimethyl-3,5-octandionate, lead (II) exafluoropentanedionate, lead (II) 2,4-pentanedionate, lead (II) 2,2,6,6-tetramethyl-3, Examples of 5-heptanedionate, lead titanium oxoacetoethoxyethoxyoxide, and alkoxide of Bi include bismuth (III) n-butoxide, bismuth (III) t-butoxide, bismuth (III) t-pentoxide, and bismuth ( III) Examples of alkoxides of hexafluoropentanedionate, bismuth (III) tetramethylheptanedionate, and Pr include praseodymium n-butoxide, praseodymium t-butoxide, praseodymium methoxypropoxide, praseodymium hexafluoropentanedionate, praseodymium 2,4-pentanedione Door, praseodymium 2,
2,6,6-tetramethyl-3,5-heptanedionate, praseodymium (III) 6,6,7,7,8,8,
Examples of alkoxides of 8-heptafluoro-2,2-dimethyl-3,5-octandionate and Nd include neodymium n-butoxide, neodymium t-butoxide, neodymium methoxy propoxide, neodymium methoxy ethoxide, and neodymium hexadeoxy. Fluoropentanedionate, neodymium 2,4-pentanedionate, neodymium 2,2,6,6-tetramethyl-3,5
-Heptandionate, neodymium trifluoropentanedionate, neodymium 6,6,7,7,8,8,8
Heptafluoro-2,2-dimethyl-3,5-octandionate, examples of alkoxides of Sm include samarium (III) isopropoxide, samarium (III)
n-butoxide, samarium (III) t-butoxide, samarium (III) methoxypropoxide, samarium (III) methoxyethoxide, samarium (II
I) 2,4-pentanedionate, samarium (III)
Examples of 2,2,6,6-tetramethyl-3,5-heptanedionate, samarium (III) tinol trifluoroacetate and alkoxide of Eu include europium n-butoxide, europium t-butoxide,
Europium methoxy propoxide, europium methoxy ethoxide, europium 2,4-pentanedionate, europium 2,2,6,6-tetramethyl-3,5-heptanedionate, europium tinol trifluoroacetate, europium 6,6 , 7,
7,8,8,8-heptafluoro-2,2-dimethyl-
Examples of 3,5-octandionate, europium 1,3-diphenyl-1,3-propanedionate, and alkoxide of Gd include gadolinium n-butoxide,
Gadolinium t-butoxide, gadolinium methoxypropoxide, gadolinium methoxyethoxide,
Gadolinium 2,4-pentanedionate, gadolinium 2,2,6,6-tetramethyl-3,5-heptanedionate, gadolinium 6,6,7,7,8,8,8-
Examples of alkoxides of heptafluoro-2,2-dimethyl-3,5-octandionate and Tb include terbium n-butoxide, terbium t-butoxide,
Terbium methoxypropoxide, terbium methoxyethoxide, terbium 2,4-pentanedionate, terbium 2,2,6,6-tetramethyl-3,5
-Examples of alkoxides of heptandionate and Dy include disprosium n-butoxide, disprosium t-butoxide, disprosium methoxypropoxide, disprosium methoxyethoxide, disprosium 2,4-pentanedionate, disprosium. Examples of alkoxides of 2,2,6,6-tetramethyl-3,5-heptanedionate and Ho include holmium n-butoxide, holmium t-butoxide, holmium methoxy propoxide, holmium methoxy ethoxide, and holmium 2 , 4-pentanedionate,
Examples of holmium 2,2,6,6-tetramethyl-3,5-heptanedionate and alkoxide of Er include:
Erbium n-butoxide, erbium t-butoxide, erbium methoxypropoxide, erbium methoxyethoxide, erbium 2,4-pentanedionate, erbium 2,2,6,6-tetramethyl-
3,5-heptanedionate, erbium 6,6,7,
7,8,8,8-heptafluoro-2,2-dimethyl-
Examples of alkoxides of 3,5-octandionate and Tm include thulium n-butoxide, thulium t-butoxide, thulium methoxypropoxide, thulium methoxyethoxide, thulium 2,4-pentanedionate, and thulium 2,2. , 6,6-tetramethyl-
Examples of alkoxides of 3,5-heptanedionate and Yb include ytterbium n-butoxide, ytterbium t-butoxide, ytterbium methoxypropoxide, ytterbium methoxyethoxide, ytterbium 2,4-pentanedionate, ytterbium 2,2 , 6,6-tetramethyl-3,5-heptanedionate, ytterbium 6,6,7,7,8,8,
Examples of octoxides of 8-heptafluoro-2,2-dimethyl-3,5-octandionate and Lu include lutetium n-butoxide, lutetium t-butoxide, lutetium methoxypropoxide, lutetium methoxyethoxide, and lutetium 2 , 4-pentanedionate, lutetium 2,2,6,6-tetramethyl-
Metal alkoxides such as 3,5-heptanedionate are exemplified. Moreover, these metal alkoxides can also be used as a polymer partially hydrolyzed and polymerized. Examples thereof include multimers of titanium isopropoxide and titanium butoxide. These metal alkoxides can be used alone or in combination of two or more.

Further, these metal alkoxides may be prepared from a corresponding metal halide (eg, titanium tetrachloride) and a corresponding alcohol (eg, n-propanol), β-diketone (eg, 2,4-pentanedione) or β-ketoester (eg, For example, the mixture may be a mixture of ethyl 3-oxobutanoate and a partially formed metal alkoxide.

Examples of the metal salt used in the present invention include:
Inorganic salts such as halides, nitrates and sulfates; salts of organic substances such as salts of phosphoric acid and salts of carboxylic acids. Examples of carboxylic acids include acrylic acid, methacrylic acid, acetic acid, salicylic acid, formic acid, oxalic acid, propionic acid, lactic acid, p-toluenesulfonic acid, trifluoroacetic acid, fumaric acid, itaconic acid, maleic acid, vinylsulfonic acid And the like.

The most preferred metal alkoxide or metal salt used in the present invention is a silicon alkoxide or a salt thereof. In the case of silicon, a carbon atom can be arranged at an adjacent position. (Silicon-containing organic compound) may be used alone or in combination as a metal alkoxide or metal salt.

Among the silicon-containing organic compounds, the high-molecular type compounds include polysilanes and polysiloxanes in which an organic group is substituted at the terminal, and a vinyl functional polysilane at one end, a vinyl functional polysilane at both ends, There are vinyl-functional polysiloxane, vinyl-functional polysiloxane at both ends, and vinyl-functional polysilane obtained by reacting these compounds.

Specific examples of the low-molecular type among the silicon-containing organic compounds include vinyltrimethoxysilane, vinyltri (β-methoxyethoxy) silane, divinyloxydimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyl Trialkoxysilane, acryloyloxyethyltriethoxysilane, glycidyloxyethyltriethoxysilane, γ-acryloyloxy-n-propyltri-n-propyloxysilane, γ-methacryloyloxy-n-propyl-n-propyloxysilane, di (Γ-acryloyloxy-n-propyl) di-
n-propyloxysilane, acryloyloxydimethoxyethylsilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl)
γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like.

Further, in the present invention, a polymerizable resin may be used in combination with the above-mentioned silicon-containing organic compound (polymer hybrid). Examples of the polymerizable resin include a polymerizable vinyl group, allyl group and acryloyl. Group, a methacryloyl group, an isopropenyl group or an epoxy group
Those having at least two are preferred. An acryloyl group, a methacryloyl group or an epoxy group is particularly preferable, and a polyfunctional monomer or oligomer having an acryl group or a methacryl group that forms a crosslinked structure or a network structure is more preferable. Acrylic urethane resin, polyester polyol acrylate and the like can be used.

The acrylic urethane resin is obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter acrylate includes methacrylate). (Only acrylate is indicated), and can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, JP-A-59-151110).

The polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate or acrylic acid with the hydroxyl group at the terminal of the polyester (for example, JP-A-59-15112). Gazette).

The epoxy acrylate resin is obtained by reacting a monomer such as acrylic acid, acrylic acid chloride or glycidyl acrylate with the hydroxyl group at the terminal of the epoxy group.

As the polyol acrylate resin,
Ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaaceritol triacrylate,
Examples thereof include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaerythritol.

As the epoxy resin, aromatic epoxy compounds (polydiglycidyl ether of polyhydric phenol),
Glycidyl ether of a reaction product of hydrogenated bisphenol A or bisphenol A and epichlorohydrin, epoxy novolak resin, and fatty acid epoxy resin include:
Aliphatic polyhydric alcohols, or polydiglycidyl ethers of their alkylene oxide adducts, polydiglycidyl, polydiglycidyl esters of aliphatic long-chain polyhydric alcohols or their alkylene oxide adducts, homopolymers of glycidyl acrylate and glycidyl methacrylate, copolymers and the like. Can be

The organic polymer used in the present invention is not particularly limited as long as it can contain silsesquioxane. The organic polymer film of the angstrom order can be obtained only by containing silsesquioxane in the organic polymer film. A membrane having pores is obtained.

Examples of these polymers include polyacrylate, polymethacrylate, aminopolyacrylamide, isobutylene maleic anhydride, AAS (acrylonitrile-acrylate-styrene copolymer), AES (acrylonitrile-ethylene-propylene-styrene copolymer), and AS (acrylonitrile −
Styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), ACS (blend of acrylonitrile-styrene copolymer and chlorinated polyethylene), MBS (methyl methacrylate-butadiene-styrene copolymer), ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer , Ethylene vinyl acetate vinyl chloride graft copolymer, ethylene vinyl alcohol copolymer, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, carboxyvinyl polymer, ketone resin, fluorinated plastic, polytetrafluoroethylene, fluorinated ethylene polypropylene copolymer, PFA (tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer), polychlorotrifluoro Ethylene, ethylene tetrafluoroethylene copolymers, polyvinylidene fluoride, polyvinyl fluoride, polyacetal, polyamide, nylon, copolymer polyamide, polyamideimide, polyarylate,
Polyetherimide, polyetheretherketone, polyethylene, polyethyleneoxide, polyethyleneterephthalate, polyvinylidene chloride, polyvinylidene chloride latex, polyvinyl chloride, polycarbonate, polyglutamic acid ester, polyvinyl acetate, polystyrene, polysulfone, polyethersulfone, polyamine Sulfone, polyparavinylphenol, polyparamethylstyrene, polyallylamine, polyvinyl alcohol,
Polyvinyl acetate, polyvinyl ether, polyvinyl butyral, polyvinyl formal, polyphenylene ether, polyphenylene sulfide, polybutadiene, polybutylene terephthalate, polypropylene, polymethylpentene, polymethyl methacrylate, epoxy resin, oligoester acrylate, xylene resin, guanamine resin, diallyl phthalate Resin, vinyl ester resin, phenol resin, unsaturated polyester resin, furan resin, polyimide, polyurethane, cellulose, cellulose acetate, celluloid, cellulose fatty acid ester, cellulose aromatic carboxylate ester, cellulose derivative, polyoxazoline, polyvinylpyrrolidone,
Representative examples thereof include polyvinyl acetate, polyethylene glycol dimethyl ether, and gelatin.

In the present invention, a cage-like silsesquioxane may be used in combination with a polymerizable resin as an organic polymer (polymer hybrid). Examples of the polymerizable resin include a polymerizable vinyl group, allyl group and acryloyl group. And those having two or more polymerizable groups such as methacryloyl group, isopropenyl group and epoxy group. An acryloyl group, a methacryloyl group or an epoxy group is particularly preferable, and a polyfunctional monomer or oligomer having an acryl group or a methacryl group that forms a crosslinked structure or a network structure is more preferable. Acrylic urethane resin, polyester polyol acrylate and the like can be used.

The acrylic urethane resin is obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter acrylate includes methacrylate). (Only acrylate is indicated), and can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate (for example, JP-A-59-151110).

The polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate or acrylic acid with the hydroxyl group at the terminal of the polyester (for example, JP-A-59-15112). Gazette).

The epoxy acrylate resin is obtained by reacting a monomer such as acrylic acid, acrylic acid chloride or glycidyl acrylate with the hydroxyl group at the terminal of the epoxy group.

As the polyol acrylate resin,
Ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaaceritol triacrylate,
Examples thereof include pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaerythritol.

As the epoxy resin, aromatic epoxy compounds (polydiglycidyl ether of polyhydric phenol),
Glycidyl ether of a reaction product of hydrogenated bisphenol A or bisphenol A and epichlorohydrin, epoxy novolak resin, and fatty acid epoxy resin include:
Aliphatic polyhydric alcohols, or polydiglycidyl ethers of their alkylene oxide adducts, polydiglycidyl, polydiglycidyl esters of aliphatic long-chain polyhydric alcohols or their alkylene oxide adducts, homopolymers of glycidyl acrylate and glycidyl methacrylate, copolymers and the like. Can be

The organic polymer used in the present invention may be used alone or in combination of two or more, and may be used in combination with the above-mentioned low molecular weight organic compound.

Further, when a metal alkoxide or a metal salt containing an aromatic group in a molecule is used, for example, when a metal oxide sol is synthesized from triethoxyphenylsilane or dichlorodiphenylsilane as a raw material, these metals may be used. It is also preferable to use a polymer having an aryl group in the main chain, which has a π-electron interaction with the bonded aryl group. Representative examples of the polymer having an aryl group in the main chain include polyethylene terephthalate, polystyrene, bisphenol A
And the like, such as polycarbonate, epoxy resin, phenol resin and diallyl phthalate resin using a polyhydric phenol as a raw material.

Further, in the present invention, any low molecular organic compound other than the organic polymer may be added.

The amount of the metal alkoxide or metal salt used in the present invention and the amount of the organic polymer used are not particularly limited as long as they are compatible with the caged silsesquioxane solution or dispersion or a single substance thereof. Preferably, the weight percentage is 0.1 to 1 relative to the cage silsesquioxane.
0000%, more preferably 10 to 1000%.

The substrate of the present invention may be any material such as metal, glass, silicon and resin, but a transparent substrate is preferred. Among them, cellulose acetate films (such as TAC and CAP), polyester films, polycarbonate films, norbonene films, polyarylate films, and polysulfone films are preferred. Particularly, a cellulose triacetate film (TAC), a cellulose acetate propionate film (CAP), a polycarbonate film, and a uniaxially stretched polyethylene terephthalate film are preferable.

The coating method of the present invention includes dipping, spin coater, knife coater, bar coater, blade coater, squeeze coater, reverse roll coater,
A known coating machine such as a gravure roll coater, a curtain coater, a spray coater, and a die coater can be used, and a method capable of continuous coating is preferably used.

Further, the cage-like silsesquioxane-containing composition of the present invention or the film coated with the same is subjected to heat treatment, light irradiation such as ultraviolet rays, or plasma treatment as necessary to improve the physical properties of the film. You may.

The use of the cage silsesquioxane-containing composition of the present invention or the film coated with the same is not particularly limited. Examples thereof include an anti-glare film, an antireflection film (anti-reflection film), a viewing angle widening film, It can be used as an optical film such as a light control film, an electromagnetic wave shielding film, and an infrared (heat ray) cut film, and a low dielectric constant material used for semiconductors such as IC and LSI.

[0080]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The evaluation method used in the examples was as follows.

(Measurement of Refractive Index) The refractive index was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.).

(Measurement of film strength) 100 g per 1 cm ²
Load on steel wool (# 0000)
The number of scratches or the state of the scratches when reciprocating was visually observed (no scratch was 10 and the sensory evaluation was a 10-step scale).

(Durability) After the sample was stored under the conditions of 80 ° C. and 90% RH for 2 weeks, the state was visually observed.

Example 1 2 g of tetraethoxysilane was dissolved in 12 g of ethanol. 2 g of 1N hydrochloric acid was added to this solution to carry out hydrolysis to prepare a sol. Compound S-1 was added to this sol in an amount of 1.0
g, and a silsesquioxane solution dissolved in 10 g of tetrahydrofuran, and stirred at 50 ° C. for 2 hours to obtain a silsesquioxane-silica composition.

This composition was spin-coated on an acrylic plate (thickness: 3 mm, refractive index: 1.49) (at 1500 rpm).
pm), followed by drying to form a cage-like silsesquioxane-containing SiO ₂ gel film. This gel film was subjected to an ultraviolet irradiation treatment for 45 seconds using an ultraviolet irradiation device 1,
A cage silsesquioxane-containing oxide film (A-1) was produced.

UV irradiation apparatus 1: UV irradiation apparatus Power supply: 3 kW Lamp: high-pressure mercury lamp Example 2 2 g of tetraethoxysilane was dissolved in 12 g of ethanol. To this solution, a solution of silsesquioxane dissolved in 1.0 g of compound S-13 and 10 g of tetrahydrofuran was added, and 0.1 g of aluminum (III) 2,4-pentanedionate was further added, followed by stirring at 50 ° C. for 2 hours. To obtain a silsesquioxane-silica composition.

This composition was spin-coated on an acrylic plate (thickness: 3 mm, refractive index: 1.49) (at 1500 rpm).
pm), followed by drying to form a cage-like silsesquioxane-containing SiO ₂ gel film. This gel film was subjected to ultraviolet irradiation for 45 seconds using the ultraviolet irradiation apparatus 1 used in Example 1 to produce a cage-like silsesquioxane-containing oxide film (A-2).

Example 3 1.0 g of compound S-12 and a solution of 2 g of polyperfluorooctyl acrylate (average molecular weight: about 20,000) in 10 g of tetrahydrofuran,
A silsesquioxane solution dissolved in 0 g was added to prepare a silsesquioxane-containing resin composition.

This composition was spin-coated on an acrylic plate (thickness: 3 mm, refractive index: 1.49) (at 1500 rpm).
pm) and then dried to form a cage-like silsesquioxane-containing resin film. An ultraviolet irradiation device 1
Was applied for 45 seconds to prepare a cage-like silsesquioxane-containing film (A-3).

Example 4 A solution prepared by dissolving 2 g of polyperfluorooctyl acrylate (average molecular weight: about 20,000) in 10 g of tetrahydrofuran was mixed with 1.0 g of compound S-14 and 1 g of tetrahydrofuran 1
A silsesquioxane solution dissolved in 0 g was added to prepare a silsesquioxane-containing resin composition.

This composition was spin-coated on an acrylic plate (thickness: 3 mm, refractive index: 1.49) (at 1500 rpm).
pm) and then dried to form a cage-like silsesquioxane-containing resin film. An ultraviolet irradiation device 1
Was applied for 45 seconds to produce a cage-like silsesquioxane-containing film (A-4).

Example 5 A solution prepared by dissolving 2 g of tetraethoxysilane in 12 g of ethanol and further dissolving 0.5 g of polyvinylpyrrolidone (average molecular weight: about 10,000) in 5 g of methanol was added. To this solution, a solution of silsesquioxane dissolved in 1.0 g of compound S-1 and 10 g of tetrahydrofuran was added, and 0.1 g of aluminum (III) 2,4-pentanedionate was further added, followed by stirring at 50 ° C. for 2 hours. To obtain a silsesquioxane-silica-polymer mixed composition.

This composition was spin-coated (at 1500 rpm) on an acrylic plate (thickness: 3 mm, refractive index: 1.49).
pm), followed by drying to form a gel film of SiO ₂ containing cage silsesquioxane and a polymer. This gel film was subjected to an ultraviolet irradiation treatment for 45 seconds using an ultraviolet irradiation device 1 to prepare a cage-like silsesquioxane-containing oxide film (A-5).

Example 6 A solution prepared by dissolving 2 g of polyperfluorooctyl acrylate (average molecular weight: about 20,000) in 10 g of tetrahydrofuran was mixed with a terminal vinyl polydimethylsiloxane DMS-V03 manufactured by Chisso Corporation (molecular weight: 500, vinyl content: 1).
(0 to 12%), a silsesquioxane solution in which 1.0 g of compound S-14 and 1.0 g of tetrahydrofuran were dissolved was added to prepare a silsesquioxane-containing resin composition.

This composition was spin-coated on an acrylic plate (thickness: 3 mm, refractive index: 1.49) (at 1500 rpm).
pm) and then dried to form a cage-like silsesquioxane-containing resin film. An ultraviolet irradiation device 1
Was applied for 45 seconds to produce a cage-like silsesquioxane-containing film (A-6).

Comparative Example 1 2 g of tetraethoxysilane was dissolved in 12 g of ethanol. 2 g of 1N hydrochloric acid was added to this solution to carry out hydrolysis to prepare a sol.

This sol solution was spin-coated on an acrylic plate (thickness: 3 mm, refractive index: 1.49) (at 1500 rpm).
pm), and dried to form a gel film of SiO ₂ . The gel film was subjected to an ultraviolet irradiation treatment for 45 seconds using the ultraviolet irradiation device 1 to produce an oxide film (R-1).

Comparative Example 2 A solution prepared by dissolving 2 g of polyperfluorooctyl acrylate (average molecular weight: about 20,000) in 10 g of tetrahydrofuran was placed on an acrylic plate (thickness: 3 mm, refractive index: 1.49).
After spin coating (at 1500 rpm), drying was performed to form a resin film. This resin film was subjected to an ultraviolet irradiation treatment for 45 seconds using an ultraviolet irradiation device 1 to obtain a resin film (R-
2) was produced.

Comparative Example 3 In a solution prepared by dissolving 2 g of polyperfluorooctyl acrylate (average molecular weight: about 20,000) in 10 g of tetrahydrofuran, vinyl-terminated polydimethylsiloxane DMS-V03 manufactured by Chisso Corporation (molecular weight: 500, vinyl content: 1)
(0 to 12%) was added to prepare a polysiloxane-containing resin composition.

This composition was spin-coated (at 1500 rpm) on an acrylic plate (thickness: 3 mm, refractive index: 1.49).
pm) and then dried to form a resin film containing polysiloxane. Using an ultraviolet irradiation device 1 on this resin film,
An ultraviolet irradiation treatment was performed for 45 seconds to produce a polysiloxane-containing resin film (R-3).

Comparative Example 4 (when non-cage silsesquioxane was used) As in Comparative Example 2, 10 g of tetrahydrofuran was mixed with polyperfluorooctyl acrylate (average molecular weight of about 2
2 g) was dissolved. A silsesquioxane solution obtained by dissolving 1 g of polymethylsilsesquioxane (SST-3M02) manufactured by Chisso Corporation in 10 g of tetrahydrofuran was added to prepare a non-cage-like silsesquioxane-containing resin composition.

This solution was spin-coated on an acrylic plate (thickness: 3 mm, refractive index: 1.49) (at 1500 rpm).
After m), drying was performed to form a resin film. This resin film was subjected to an ultraviolet irradiation treatment for 45 seconds using the ultraviolet irradiation device 1 to produce a resin film (R-4).

Table 1 shows Examples 1 to 6 and Comparative Example 1.
The physical property values of the coating films prepared on the acrylic plate in Comparative Example 4 are shown.

[0105]

[Table 1]

As is clear from the results shown in Table 1, the film containing the cage-like silsesquioxane of the present invention has a binder of silica (A-1, A-2) and an organic polymer (A-
3, A-4), organic polymer composite silica (A-
5) and organic polymer composite silicone (A-
In any of the cases 6), a decrease in the refractive index, an increase in the film strength, and an improvement in the durability are observed as compared with the films (R-1, R-2, R-3) containing no cage silsesquioxane. Was. The film (R-4) containing polymethylsilsesquioxane, a non-cage-like silsesquioxane, showed an increase in film strength and an improvement in durability, but was the most important factor in this study. No decrease in the refractive index was observed at all.

From these results, it can be seen that in the cage-like silsesquioxane-containing film of the present invention, the molecular-level vacancies of the cage-like silsesquioxane function effectively to lower the refractive index. Was revealed. That is,
Conversely, by including a cage-like silsesquioxane, it is possible to easily produce microvoids in the film,
As a result, the refractive index decreases. Naturally, if a film having a low refractive index is formed, it can be used as an optical film for antireflection, and the dielectric constant, which is a physical property related to the refractive index, is naturally lowered. That is, in the present invention, by coating a cage-like silsesquioxane on a base material with a certain binder, a film having a low refractive index or a low dielectric constant can be produced, and an optical property improving film such as an antireflection film can be formed. It was found that the film could be produced, and that the film strength and durability of the film could be improved.

Example 7 The coating liquid prepared in Example 3 was applied to a triacetyl cellulose base (80 μm in thickness) coated with a 3 μm-thick acrylic resin hard coat by a wire bar to a wet film thickness of 15 μm.
After coating and drying at μm, ultraviolet irradiation treatment was performed in the same manner as in Example 3 to prepare an antireflection film (AR-1).

For comparison, the coating solution prepared in Comparative Example 2 was applied under the same conditions as AR-1 described above, and the same treatment was carried out to prepare a comparative antireflection film (AR-2).

The reflectivity of the two types of antireflection films was 4
Measurements were taken at 50 nm and 650 nm.

Table 2 shows the results.

[0112]

[Table 2]

As is clear from the results shown in Table 2, the antireflection film (AR-1) coated with the cage-like silsesquioxane-containing coating film of the present invention was a comparative sample (AR-2).
It was found that the reflectance was significantly reduced as compared with that of Example 1, and that the composition had excellent antireflection performance.

Example 8 Example 1 was repeated except that tetraethoxysilane of Example 1 was replaced with the same weight of the following metal alkoxide or metal salt.
A metal oxide-containing coating solution was prepared in exactly the same manner as in
The coating was performed under the same conditions as in

Further, a metal oxide-containing coating solution was prepared in exactly the same manner as in Comparative Example 1 except that tetraethoxysilane of Comparative Example 1 was replaced with the same weight of a metal alkoxide or metal salt shown below. It was applied under the same conditions.

The coated sample thus obtained was treated under the same conditions as in Example 1 and the refractive index was measured by the same method as in Examples 1 to 6.

As a result, it was confirmed that all the metal oxide films containing the cage silsesquioxane showed a significant decrease in the refractive index as compared with the corresponding films not containing the cage silsesquioxane.

Metal alkoxide or metal salt 4-1 Aluminum tri-n-butoxide 4-2 Tetraisopropoxytitanium 4-3 Zinc 2,4-pentanedionate 4-4 Strontium 2,4-pentanedionate 4-5 Yttrium Isopropoxide 4-6 zirconium-n-pyroxide 4-7 magnesium ethoxide 4-8 tetra-t-butoxytin 4-9 calcium hexafluoropentanedionate 4-10 europium 2,4-pentanedionate 4-11 terbium 2 , 4-Pentandionate 4-12 Antimony butoxide 4-13 Niobium chloride

[0119]

By coating a cage-like silsesquioxane on a substrate, a film having a low refractive index can be produced, and a film having improved optical properties such as an antireflection film can be produced. It was found that the film strength and durability were also improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/057 C08K 5/057 4J002 5/09 5/09 4J035 C08L 83/04 C08L 83/04 4J038 101 / 16 C09D 7/12 Z C09D 7/12 183/04 183/04 201/00 201/00 C07F 7/18 X // C07F 7/18 7/21 7/21 C08J 5/18 CFH C08J 5/18 CFH C08L 101/00 F-term (reference) 4F071 AA01 AA67 AB18 AC05 AC09 AH19 BA03 BC02 4F100 AA02B AH06B AH08B AK01B AK25A AT00A BA02 CA30B CA30H CC01B EH46 EJ54 GB41 JD06 JM01B JN01A JN08 FA05A05FAN FF07 FF09 GG02 HH28 HH30 JJ14 LL11 LL15 MM02 NN21 PP01 PP03 PP17 UU01 4H049 VN01 VP08 VP09 VP10 VQ02 VQ03 VQ07 VQ26 VQ48 VQ78 VQ86 VQ88 VR11 VR21 VR43 VR44 VS 02 VS03 VS07 VS26 VS48 VS78 VU29 4J002 AB012 AC032 BB032 BB062 BB122 BB242 BC062 BC082 BD042 BD062 BD102 BD122 BD142 BD152 BD172 BE022 BE032 BE042 BE052 CF062 BF022 BG042 BG062 BG122 CB122 BN122 CB122 BN122 CB122 CG002 CH022 CH092 CK023 CL002 CM042 CN032 CP012 CP031 CP142 DD026 DF036 DG046 DH046 EC076 EG046 EG056 EG106 EX036 EX066 EX076 EX086 GP00 4J035 BA12 CA01K CA022 CA072 CA102 CA112 CA132 CA142 CA152 CA172 CA01 CA262 LA074 KA12 NA11 NA17 PB08 PC02 PC03 PC08

Claims (11)

[Claims] 1. A film having a film containing at least one kind of cage silsesquioxane on a transparent substrate. 2. The film according to claim 1, wherein the cage-like silsesquioxane is a compound represented by the following general formulas (1) to (7). Embedded image Embedded image (In the formula, R represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and a plurality of Rs may be the same.) 3. A composition characterized by being a metal oxide sol or a metal oxide gel containing at least one kind of cage silsesquioxane in at least one kind of metal alkoxide or metal salt. 4. Applying a metal oxide sol or a metal oxide gel composition comprising at least one metal alkoxide or metal salt and at least one cage silsesquioxane contained on a substrate. A cage-like silsesquioxane-containing film formed by: 5. A method for applying a metal oxide sol or a metal oxide gel composition comprising at least one metal alkoxide or metal salt and at least one cage silsesquioxane to a substrate. A method for producing a cage-like silsesquioxane-containing coating, characterized in that: 6. A resin composition characterized in that at least one kind of organic polymer contains at least one kind of cage silsesquioxane. 7. A cage formed by applying a resin composition containing at least one cage silsesquioxane to at least one organic polymer on a substrate. Silsesquioxane-containing coating. 8. A cage-like silsesquioxane-containing resin composition comprising applying a resin composition comprising at least one kind of organic polymer and at least one kind of cage-like silsesquioxane on a substrate. Manufacturing method of the film. 9. A metal oxide sol or metal oxide in which a film containing a cage silsesquioxane contains at least one cage silsesquioxane in at least one metal alkoxide or metal salt. Gel composition,
The film according to claim 1, wherein the film is formed by coating on a transparent substrate. 10. The method of claim 1, wherein the film containing the cage silsesquioxane comprises at least one organic polymer and at least one organic polymer.
3. The film according to claim 1, wherein the resin composition containing a kind of cage-like silsesquioxane is formed by coating on a transparent substrate. 4. 11. A polymer comprising a cage silsesquioxane containing at least one metal alkoxide or metal salt and at least one organic polymer containing at least one cage silsesquioxane. The composite metal oxide sol or the polymer composite metal oxide gel composition is formed by coating on a transparent substrate.
The film according to 1.