JP2002122704A - High refractive index thin film and antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin film formable by a wet method such as coating, having a refractive index higher than that of a conventional resin-base thin film and also having good water repellency. SOLUTION: The high refractive index thin film comprises a polysilane of formula (1) [where R is H, hydroxyl, alkyl, alkenyl, arylalkyl, aryl, alkoxyl or silyl, all of plural symbols R are the same, or two or more of these are different from each other, (x), (y) and (z) are each a number >=0 and x+y+z=5 to 400].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an optical filter,
The present invention relates to a high refractive index thin film for use in various optical articles such as lenses and waveguides, and more particularly to a resin-based high refractive index thin film formed by a wet method such as coating. Further, the present invention relates to an antireflection film formed on a front surface of a liquid crystal display (LCD), a cathode ray tube display (CRT), a plasma display (PDP), and other display screens.

[0002]

2. Description of the Related Art As a material for forming a high refractive index thin film used for various optical articles, titanium oxide, zirconium oxide,
Metal oxides such as tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, yttrium oxide, ytterbium oxide, and indium tin oxide are usually used. However, in order to form these metal oxides into a thin film, a vacuum evaporation method, a reactive evaporation method, an ion beam assisted evaporation method, a sputtering method, an ion plating method, a plasma CV
Since a vacuum film forming process such as method D is required, it is difficult to increase the area of the thin film, and the productivity is poor.

On the other hand, as a material for forming a high refractive index thin film that does not require a vacuum film forming process, organic resin materials such as polycarbonate resin and aromatic polyester resin capable of forming a thin film by a wet method are exemplified. The rates are not high enough. Further, these resin-based thin films have poor water repellency, and thus have a drawback that they are easily stained.

[0004] Therefore, a high refractive index thin film which has a high refractive index and is excellent in water repellency, which is a resin system which can be formed by a wet method such as a coating method, is required.

[0005] One of the applications of the high refractive index thin film is as follows.
Examples include an antireflection film formed on the front surface of a display screen such as a liquid crystal display, a cathode ray tube of a television or computer, and a plasma display. This antireflection film is obtained by sequentially laminating a low refractive index thin film and a high refractive index thin film.

This high-refractive-index thin film is usually formed by a metal oxide vacuum film forming process. However, with the recent expansion of display screens, there is a need for an antireflection film that is obtained by using a resin-based material that can be easily formed into a large area by a wet method and has antifouling properties.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and can be formed by a wet method such as coating, and has a higher refractive index than conventional resin-based thin films. It is an object of the present invention to provide a thin film having high water repellency at a high efficiency. Further, it is another object of the present invention to provide an antireflection film which is formed by a wet method that can be easily enlarged and has antifouling properties.

[0008]

As a result of intensive studies, the present inventors have found that the above object can be achieved by using a polysilane thin film and a polysilane-based cured film, and have completed the present invention.

That is, the present invention provides a high refractive index thin film and an antireflection film described below. Item 1. General formula (1)

[0010]

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[In the formula, R represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxyl group or a silyl group. All of R may be the same or two or more may be different. x,
y and z each represent a number of 0 or more, and x, y and z
Is 5 to 400. ] The high refractive index thin film which consists of polysilane represented by these. Item 2. General formula (1)

[0012]

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Wherein R represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxyl group or a silyl group. All of R may be the same or two or more may be different. x,
y and z each represent a number of 0 or more, and x, y and z
Is 5 to 400. And a high-refractive-index thin film obtained by heat-treating a mixture of a polysilane having a hydroxyl group at a terminal and a thermosetting resin raw material. Item 3. Item 2 wherein the thermosetting resin material is an epoxy compound
2. The high refractive index thin film according to 1. Item 4. General formula (1)

[0014]

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[Wherein, R represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxyl group or a silyl group. All of R may be the same or two or more may be different. x,
y and z each represent a number of 0 or more, and x, y and z
Is 5 to 400. A polysilane represented by the formula:
A high-refractive-index thin film obtained by subjecting a mixture with a photocurable resin raw material to an exposure treatment. Item 5. Item 5. An antireflection film using the high refractive index thin film according to any one of items 1 to 4.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Polysilane] The polysilane used in the present invention is represented by the following general formula (1).

[0017]

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In the formula, R represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group,
It represents an alkoxyl group or a silyl group. All of R may be the same or two or more may be different. x, y,
z represents a number of 0 or more, respectively, and the sum of x, y, and z is 5 to 400.

In the polysilane represented by the above general formula (1), the alkyl group, the alkyl part of the arylalkyl group and the alkyl part of the alkoxyl group are preferably linear, cyclic or branched, having 1 to 14 carbon atoms. Is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

As the alkenyl group, a monovalent linear, cyclic or branched C1-C14 having at least one carbon-carbon double bond, preferably C1-C10,
More preferably, an aliphatic hydrocarbon group having 1 to 6 carbon atoms is used.

Examples of the aryl group and the aryl moiety of the arylalkyl group include an aromatic hydrocarbon group which may have at least one substituent, and preferably has at least one substituent. Examples include a phenyl group or a naphthyl group. The substituent of the aryl part of the aryl group and the arylalkyl group is not particularly limited, but is preferably at least one selected from the group consisting of an alkyl group, an alkoxyl group, an amino group and a silyl group.

In the polysilane represented by the above general formula (1), it is generally preferable to use R having a phenyl group because the refractive index of the thin film is improved.

As the polysilane used in the present invention,
In particular, when a mixture with a thermosetting resin material is heat-treated to form a thermosetting resin, a polysilane having at least one hydroxyl group directly bonded to a terminal Si atom (ie, a polysilane having at least one silanol group at a terminal) ). The hydroxyl group directly bonded to the Si atom shows good reactivity with the functional group of the thermosetting resin material, for example, an epoxy group, and a heat treatment forms a crosslinked structure between the polysilane and the thermosetting resin material. You.

The content ratio of such a hydroxyl group is usually about 0.01 to 3, preferably about 0.1 to 2.5, more preferably about 0.2 to 2 on average per 1 atom of Si. Particularly preferably, the average is about 0.3 to 1.5.

The polysilane having a hydroxyl group as described above includes, in the above general formula (1), y> 0 and / or
Or a polysilane having a branched structure and / or a network structure in which z> 0 is more preferable. Such a polysilane has good compatibility with the thermosetting resin raw material, and when it is formed into a cured film, the hardness, heat resistance, chemical resistance, and the like are improved.

[Production Method of Polysilane] The polysilane used in the present invention can be produced by a known method. For example, a monomer having each structural unit can be used as a raw material and polymerized by the following method.
That is, a method of dehalogenating polycondensation of halosilanes in the presence of an alkali metal ("Kipping method" J. Am. Chem.
Soc., 110, 124 (1988), Macromolecules, 23, 3423 (199
0)), a method of dehalogenating polycondensation of halosilanes by electrode reduction (J. Chem. Soc., Chem. Commun., 1161 (1990),
J. Chem. Soc., Chem. Commun., 897 (1992)), a method of dehalogenating polycondensation of halosilanes using magnesium as a reducing agent (International Publication No. WO98 / 29476), hydrosilanes in the presence of a metal catalyst. A method of dehydrocondensation polymerization (JP-A-4-334551), a method of anionic polymerization of disilene cross-linked with biphenyl or the like (Macrom
olecules, 23, 4494 (1990)) and a method by ring-opening polymerization of cyclic silanes.

A known method can be used for introducing a hydroxyl group into the polysilane. For example, in a method of dehalogenating polycondensation of halosilanes, the reaction can be easily performed by adding water at the end of the polycondensation reaction.

[Thermosetting Resin Raw Material] The high refractive index thin film of the present invention comprises a polysilane having at least one hydroxyl group directly bonded to a terminal Si atom (that is, a polysilane having at least one silanol group at a terminal) and a thermosetting resin. It can be obtained by heat-treating a mixture with a conductive resin raw material to form a thermosetting resin. This improves the mechanical strength of the thin film,
It becomes a thin film having more excellent durability. Such a thermosetting resin raw material is not particularly limited as long as the thin film after curing has transparency, but is preferably an epoxy compound, an isocyanate compound, a cyanate compound, an acrylate compound, a vinyl compound, a bismaleimide resin, or a phenol. Resins.

The mixing ratio of the polysilane and the thermosetting resin material is about 0.01 to 100 parts by weight, preferably 0.05 part by weight, per 1 part by weight of the thermosetting resin material.
About 20 parts by weight, more preferably about 0.1 to 10 parts by weight, particularly preferably about 0.2 to 3 parts by weight.

Among the above thermosetting resin raw materials, epoxy compounds can be suitably used. The epoxy compound is a compound having at least one epoxy group in the compound. The structure of the epoxy compound is not particularly limited, and may be linear,
Examples thereof include a cyclic shape and a branched shape.

Examples of such epoxy compounds include epi-bis glycidyl ether, phenol novolak glycidyl ether, cresol novolac glycidyl ether, brominated glycidyl ether, nitrogen-containing epoxy compound, glycidyl ester, and peracetic acid oxidation epoxy compound. Glycidyl ether, silicon-containing epoxy compounds, fluorene-containing epoxy compounds, and acryl or methacryl-modified epoxy compounds of these compounds. For these compounds,
The structures of typical compounds are shown below (Chemical Formulas 8 to 1).
2). Furthermore, bisphenoxyethanol full orange glycidyl ether, bisphenol full orange glycidyl ether, 1,2,3,4-diepoxybutane,
Examples include 1,4-cyclohexanedimethanol diglycidyl ether, N, N-diglycidyl-4-glycidyloxyaniline, 1,2,5,6-diepoxycyclooctane, and the like. These epoxy compounds are
One type or a mixture of two or more types can be used. These compounds can be appropriately selected depending on the purpose, application, and the like.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[Photocurable Resin Raw Material] In the present invention, a mixture of polysilane and photocurable resin raw material can be exposed to light to obtain a photocurable resin. Such a photocurable resin raw material is not particularly limited as long as the thin film after curing has transparency, but a vinyl compound or an acrylate compound can be suitably used.

The polysilane in this case may be a polysilane in which at least one hydroxyl group is directly bonded to a terminal Si atom, or a polysilane having no such hydroxyl group.

The mixing ratio of the polysilane and the photocurable resin material is about 0.01 to 100 parts by weight, preferably 0.05 part by weight, per 1 part by weight of the photocurable resin material.
About 20 parts by weight, more preferably about 0.1 to 10 parts by weight, particularly preferably about 0.2 to 3 parts by weight.

[Curing Agent, Curing Accelerator, etc.] In the high refractive index thin film of the present invention, a thermosetting resin and / or a photocurable resin is formed from polysilane and a thermosetting resin material and / or a photocurable resin material. In this case, a curing agent or a curing accelerator may be used as necessary. The curing agent or curing accelerator is not particularly limited as long as it is a curing accelerator or the like usually used in the art. For example, silicon compounds such as polyalkoxysilanes such as 1,2-disilylethane, ethylsilicate and methylsilicate; titanium compounds such as tetraalkoxytitanium; boron compounds such as phenyldichloroborane; benzoyl peroxide;
compounds generating radicals such as rt-butyl peroxide and azoisobutyronitrile; organic aluminum compounds such as trismethoxyaluminum and trisphenoxyaluminum; triethylamine, pyridine, diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, tris Amine compounds such as (dimethylaminomethyl) phenol and 2-ethyl-4-methylimidazole; amide compounds such as dimer acid polyamide; phthalic anhydride, tetrahydromethyl phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and methyl anhydride Acid anhydrides such as nadic acid; phenols such as phenol novolak; mercaptan compounds such as polysulfide; boron trifluoride / ethylamine complex Lewis acid complex compounds, such as can be exemplified basic compounds such as sodium ethoxide and the like; chloroform, dichloromethane, halides such as trichloromethane. When performing the exposure treatment, an aromatic diazonium salt, a diallyliodonium salt, a triallylsulfonium salt, a photodegradable curing agent such as a triallylselenium salt can be used, benzophenone and its derivatives, o-benzoyl benzoate and its derivatives. Derivatives, acetophenone and its derivatives, benzoin, benzoin ether and its derivatives, xanthone and its derivatives, thioxanthone and its derivatives,
Examples include disulfide compounds, quinone compounds, compounds containing halogenated hydrocarbon groups, amines, and photosensitizers such as dyes. These curing agents or curing accelerators can be used alone or in combination of two or more.

The amount of the curing agent or the curing accelerator may be appropriately set depending on the kind and ratio of the polysilane to be used, as long as the effect of the present invention is not impaired. The amount of these additives is usually about 150 parts by weight or less, preferably about 100 parts by weight or less, based on 100 parts by weight of the thermosetting resin material or the photocurable resin material.

Further, the high refractive index thin film of the present invention may contain various fillers and additives usually used in the art, if necessary, and the mixing amount thereof does not impair the effects of the present invention. What is necessary is just to set suitably in a range.

[Manufacturing Method of High Refractive Index Thin Film] An example of a method of manufacturing the high refractive index thin film of the present invention will be described below.

First, a coating solution is prepared. Polysilane and, if necessary, a thermosetting resin material, a photocurable resin material, a filler and an additive are dissolved or uniformly dispersed in a solvent. The solvent varies depending on the substituents of each compound, and examples include toluene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, and a mixed solvent thereof. be able to.

However, if the polysilane or resin material is liquid and the above components can be dissolved or uniformly dispersed, a coating solution may be prepared without using a solvent.

This coating solution is applied onto various substrates by spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, or the like.

Next, a drying treatment of the coated material is performed as required. The drying treatment is performed under normal pressure, under pressure, or under reduced pressure, at normal temperature or by heating.

In the present invention, a heat treatment for heat curing is performed as required. The drying treatment and the heat treatment may be performed sequentially, or may be performed collectively for both the drying treatment and the heating treatment. The heating temperature range of the heat treatment in the production of the high refractive index thin film of the present invention is 50 to 500 ° C, preferably 80 to 450 ° C, more preferably 100 to 400 ° C.
It is. The time for maintaining the above temperature is 1 minute to 48 hours, preferably 3 minutes to 24 hours, more preferably 5 minutes to 18 hours.

The heat treatment may be performed by dividing into a plurality of steps, or may be performed by arbitrarily combining a temperature raising step, a step of maintaining a constant temperature, and a temperature lowering step. The rate of temperature increase and decrease is not particularly limited, but is 0.1 ° C./min to 50 ° C.
/ Sec is preferred.

In the present invention, an exposure process for photo-curing is performed as necessary. Although the light source is not particularly limited, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a deuterium lamp, a halogen lamp, a helium-cadmium laser, an excimer laser, or the like is used. Exposure energy is usually 1 mJ / cm ^{2 to} 100 J / cm ² ,
Preferably, it is about 10 mJ / cm ^{2 to} 10 J / cm ² .

The exposure treatment and the heat treatment may be used in combination.
In this case, the order of the exposure treatment and the heat treatment is not particularly limited, but usually, the heat treatment is performed after the exposure treatment.

[Method of Manufacturing Antireflection Film] Next, an example of a method of manufacturing an antireflection film using the high refractive index thin film of the present invention will be described.

The principle of a general multilayer antireflection film and its film forming method are already known, and various methods and examples have been introduced according to various purposes. A transparent thin film with a refractive index smaller than the refractive index of a glass substrate or a resin film, and a transparent thin film with a refractive index larger than the refractive index of a substrate are designed so that the overall reflectance is close to a minimum. Optical film thickness (product of refractive index n and absolute thickness d).

At this time, the high refractive index thin film is formed by the above-described method.

On the other hand, as a material for forming the low refractive index thin film,
Silicon oxide, magnesium fluoride, calcium fluoride,
An inorganic compound such as barium fluoride can be used.
In addition, organic resins such as fluorine-based, acrylic-based, urethane-based, polyester-based, and melamine-based resins can be used.

As a method for forming the low refractive index thin film, when an inorganic compound is used, a vacuum evaporation method, a reactive evaporation method,
A vacuum film forming process such as an ion beam assisted vapor deposition method, a sputtering method, an ion plating method, and a plasma CVD method can be used. Also, when using an organic resin, after performing a wet method such as spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, etc. The organic resin can be formed by performing a drying treatment, a heating treatment, an exposure treatment, and the like, and a method optimal for the properties such as coatability and curability of each organic resin is appropriately selected.

[High-refractive-index molded body] In the above, the high-refractive-index thin film and the antireflection film using the same have been described. It can also be a rate molded article.

The polysilane and, if necessary, the thermosetting resin material, the photocurable resin material, fillers and additives are dispersed and mixed using a mixing tank equipped with a heating device, a kneader, an extruder, a roll, or the like. Thereby, a resin composition is obtained. Thereafter, a high refractive index molded article can be obtained by using a known method such as compression molding, casting molding, transfer molding, sheet molding, or injection molding.

Such a molded article having a high refractive index can be suitably used for a lens, a prism, a core portion of an optical fiber, a diffraction grating and the like.

Further, in the present invention, in addition to the thin film and the molded product,
It can also be used as an optical path connection adhesive. The adhesive for optical path connection requires transparency and the matching of the refractive index with the optical path, but polysilane, which is an essential component of the present invention, has a high refractive index. Or the refractive index of the core material of the optical waveguide. Examples of such a low refractive index material include a fluorine-based epoxy resin. Applications of the optical path connection adhesive include bonding between optical fibers,
Adhesion between an optical waveguide / optical modulator and an optical fiber, fixing of an optical element such as an optical filter, and the like are included. In order to improve the bonding strength, it is preferable to perform heat curing or light curing treatment.

The high refractive index thin film of the present invention can be suitably used for applications such as an optical waveguide, a microlens array, a light scattering film, an optical filter, and a diffraction element, in addition to the above-described antireflection film. Among these applications, the optical waveguide and the microlens array should be manufactured by utilizing the phenomenon that the refractive index of the polysilane, which is essential for forming the high-refractive-index thin film of the present invention, is significantly reduced when irradiated with sensitive light. Can be.

The optical waveguide can be manufactured by the following steps. That is, after applying a resin composition for forming a high refractive index thin film of the present invention on a substrate having a smaller refractive index than the high refractive index thin film of the present invention, a photomask is applied to a portion corresponding to a core. Then, only the portion corresponding to the clad is irradiated with light in a wavelength band in which the polysilane has photosensitivity. As a result, the refractive index of the polysilane is reduced only in the irradiated portion, and a clad is formed. The wavelength band of such light varies depending on the structure of the polysilane, but is usually in the ultraviolet region. The light irradiation for changing the refractive index can be performed before or after the heat-curing or light-curing treatment, but is preferably performed before the curing treatment in terms of sensitivity. In the case of photocuring, it is preferable that the exposure wavelength for the curing treatment is longer than the wavelength at which the polysilane has sensitivity, because the change in the refractive index during the photocuring treatment can be suppressed.

The microlens array can be manufactured by the following steps, similarly to the optical waveguide. That is, after applying the resin composition for forming the high refractive index thin film of the present invention on a base material, the film is irradiated with light having an intensity distribution in the plane direction of the film using a mask or the like, so that it is refracted. By forming a refractive index distribution, a gradient index lens or a lens array can be formed. The sensitivity can be improved by forming the microlens array on a pixel of a solid-state imaging device of a digital camera or a video camera. Further, the present lens array can be suitably used for a liquid crystal display device.

The light scattering film can be manufactured by forming a fine refractive index pattern in the same manner as the micro lens array. Such a light scattering film can be used as a diffusion film of a backlight of a liquid crystal display.

The optical filter can be formed by forming a laminate with a plurality of thin films having different refractive indexes from the high refractive index thin film of the present invention. At this time, the refractive index and the film thickness of each layer may be appropriately selected according to the required wavelength dispersion characteristics of the optical filter. The present optical filter may be formed on a substrate such as a film or a sheet, or may be formed directly on a surface layer of an optical component such as a lens or a prism.

[0066]

EXAMPLES Hereinafter, various examples will be described in order to explain the present invention in more detail. The present invention is not limited to these examples.

Example 1 Poly (methylphenylsilane) (weight average molecular weight: 180
00) 1 part by weight was dissolved in 9 parts by weight of toluene to prepare a coating solution. This coating solution is applied to a non-alkali glass substrate (N
o. 1737; manufactured by Corning) and dried in air at 100 ° C. for 1 hour to obtain a transparent thin film having a thickness of 300 nm.

The refractive index of the obtained thin film was measured by a light interference type film thickness meter. The water repellency was evaluated by measuring the contact angle of water. Table 1 shows the results.

Example 2 Instead of poly (methylphenylsilane), a hydroxyl-terminated poly (phenylsilin) (weight average molecular weight 170
A thin film was prepared in the same manner as in Example 1 except that 0) was used.
evaluated. Table 1 shows the results.

Example 3 1 part by weight of a poly (phenylsiline) having a terminal hydroxyl group (weight average molecular weight: 1700) and 1 part by weight of a cresol novolak type epoxy resin (ECN1299; manufactured by Asahi Ciba) were mixed with ethyl cellosolve acetate (ethylene glycol monoethyl). The solution was dissolved in 12 parts by weight of ether acetate to prepare a coating solution A. This coating solution is spin-coated on a non-alkali glass substrate (No. 1737; manufactured by Corning), heated in air at 80 ° C. for 1 hour, and then heated to 200 ° C. in 45 minutes (heating rate about 2.7 ° C.). / Min), and then heat-treated at 200 ° C. for another 1 hour.
A transparent thin film having a thickness of 400 nm was obtained.

The refractive index of the obtained thin film was measured by a light interference type film thickness meter. The water repellency was evaluated by measuring the contact angle of water. Table 1 shows the results.

Example 4 1 part by weight of hydroxyl-terminated poly (phenylsilin) (weight average molecular weight 1700), an ultraviolet-curable epoxy acrylate paint (Unidick V-5502; manufactured by Dainippon Ink and Chemicals, Inc.) One part by weight and 0.1 part by weight of a photopolymerization initiator (Irgacure 907; manufactured by Ciba Specialty Chemicals Co., Ltd.) are dissolved in 12 parts by weight of ethyl cellosolve (ethylene glycol monoethyl ether) to prepare a coating solution. did. This coating solution was spin-coated on an alkali-free glass substrate (No. 1737; manufactured by Corning), dried at room temperature for 30 minutes, and then cured by irradiating light of 1 J / cm ² with an ultra-high pressure mercury lamp. Thus, a transparent thin film having a thickness of 400 nm was obtained.

The refractive index of the obtained thin film was measured by a light interference type film thickness meter. The water repellency was evaluated by measuring the contact angle of water. Table 1 shows the results.

Example 5 1 part by weight of poly (phenylsilin) having a hydroxyl group at a terminal (weight average molecular weight 1700) and bisphenoxyethanol full orange glycidyl ether

[0075]

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One part by weight (epoxy equivalent: 293) was dissolved in 12 parts by weight of ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate) to prepare a coating solution. This coating solution is applied to a non-alkali glass substrate (N
o. 1737; Corning) and heated in air at 80 ° C. for 1 hour, then at 200 ° C. for 45 minutes
To 200 ° C after heating up to about 2.7 ° C / min.
And further heat treatment for 1 hour to obtain a film thickness of 400 n
m transparent thin film was obtained.

The refractive index of the obtained thin film was measured by a light interference type film thickness meter. The water repellency was evaluated by measuring the contact angle of water. Table 1 shows the results.

Example 6 Bisphenoxyethanol full orange acrylate was used in place of 1 part by weight of bisphenoxyethanol full orange glycidyl ether.

[0079]

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A thin film was prepared and evaluated in the same manner as in Example 5 except that 1 part by weight was used. Table 1 shows the results.

Example 7 Bisphenoxyethanol Full Orange Glycidyl Ether Instead of 1 part by weight of bisphenoxyethanol full orange glycidyl ether

[0082]

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A thin film was prepared and evaluated in the same manner as in Example 5 except that 1 part by weight (epoxy equivalent: 243) was used. Table 1 shows the results.

Example 8 Hydroxy-terminated phenylsiline (0.7) methylphenylsilane (0.3) copolymer instead of 1 part by weight of poly (phenylsilin) having a hydroxyl group at the terminal (weight average molecular weight 1700) A thin film was prepared and evaluated in the same manner as in Example 5, except that 1 part by weight of the coalesced substance (weight average molecular weight 2000) was used. Table 1 shows the results.

Comparative Example 1 A thin film was prepared and evaluated in the same manner as in Example 1 except that polycarbonate (Iupilon PCZ-300; manufactured by Mitsubishi Gas Chemical) was used instead of poly (methylphenylsilane). Table 1 shows the results.

Comparative Example 2 [0086] Except that 1 part by weight of methyltetrahydrophthalic anhydride (Epicure YH300; manufactured by Yuka Shell Epoxy) was used in place of 1 part by weight of poly (phenylsilin) having a hydroxyl group at a terminal (weight average molecular weight 1700). Prepared and evaluated a thin film in the same manner as in Example 3. Table 1 shows the results.

[0087]

[Table 1]

Example 9 0.1 part by weight of a radical copolymer of perfluoro (2,2-dimethyl-1,3-dioxole) and perfluoro (butenyl vinyl ether) was used as a fluorine-based low refractive index resin. Dissolved in 10 parts by weight of octane,
A coating solution was prepared. This coating liquid was spin-coated on a non-alkali glass substrate (No. 1737; manufactured by Corning) and heat-treated at 100 ° C. for 10 minutes in air to obtain a transparent thin film having a refractive index of 1.32.

Next, the coating liquid A described in Example 3 was spin-coated on the thin film, heated in air at 80 ° C. for 1 hour, and then heated to 200 ° C. in 45 minutes (heating rate about 2.7). (° C./min), and then heat-treated at 200 ° C. for 1 hour to obtain an antireflection film.

When the single-sided light reflectance before and after the formation of the antireflection film was measured, the single-sided light reflectance of the glass substrate before the formation of the antireflection film was 4.1%. Was 0.6%, and a good antireflection effect was obtained.

[0091]

The high refractive index thin film of the present invention can be formed by a wet method, has a high refractive index, and has good water repellency. In addition, surface hardness, adhesion,
It also has weather resistance, abrasion resistance and crack resistance.

Further, the antireflection film of the present invention has a sufficient antireflection function, has antifouling properties, and is excellent in productivity.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Hiroki Sakamoto 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Inside Osaka Gas Co., Ltd. (72) Inventor Shinichi Kawasaki 4-chome, Hirano-cho, Chuo-ku, Osaka-shi, Osaka No. 1-2 F-term in Osaka Gas Co., Ltd. (reference) 2K009 AA02 CC03 CC06 CC33 CC42 DD02 DD03 DD04 DD05 EE05 4F100 AG00A AH01B AK01B AK52B AK53B BA02 BA07 EH46 GB41 JB13B JN18 JN30

Claims (5)

[Claims] 1. A compound of the general formula (1) [In the formula, R represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxyl group or a silyl group. All of R may be the same or two or more may be different. x, y, and z each represent a number of 0 or more, and the sum of x, y, and z is 5 to 40.
0. ] The high refractive index thin film which consists of polysilane represented by these. 2. A compound of the general formula (1) [In the formula, R represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxyl group or a silyl group. All of R may be the same or two or more may be different. x, y, and z each represent a number of 0 or more, and the sum of x, y, and z is 5 to 40.
0. And a high-refractive-index thin film obtained by heat-treating a mixture of a polysilane having a hydroxyl group at a terminal and a thermosetting resin raw material. 3. The high refractive index thin film according to claim 2, wherein the thermosetting resin material is an epoxy compound. 4. A compound of the general formula (1) [In the formula, R represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxyl group or a silyl group. All of R may be the same or two or more may be different. x, y, and z each represent a number of 0 or more, and the sum of x, y, and z is 5 to 40.
0. ], A high-refractive-index thin film obtained by subjecting a mixture of the polysilane represented by the formula (1) and a photocurable resin raw material to an exposure treatment. 5. An antireflection film comprising the high refractive index thin film according to claim 1.