JP2000198964A - Optically functional film and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation method for an optically functional film which uses a coating process with no heating steps, yields a gel thin film having a low refractive index of 1.38 to 1.46 and has advantages of large-scale production and low equipment cost, and an optically functional film obtained through this preparation method. SOLUTION: An optically functional film comprises a gel layer supported directly on a substrate or via other layers. The optically functional film is prepared by producing an applied layer from an alkoxy silane hydrolysate solution, prepared by hydrolyzing a silicon alkoxide of the formula: RmSi(OR')n (wherein R is an 1-10C alkyl group or a reactive group such as a vinyl group, a (meth)acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group, a carboxyl group or the like; R' is an 1-10C alkyl group; and m+n is an integer of 4), through an application method (solution method), and subsequently curing the applied layer by an active energy ray (e.g. ultraviolet ray) to yield an organopolysiloxane layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ultraviolet shielding effect,
The present invention relates to various optical functional films having a heat ray reflection effect, an antireflection effect, and the like, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, an ultraviolet blocking effect, a heat ray reflecting effect,
In general, a method of forming a functional thin film having an antireflection effect is roughly classified into a gas phase method and a coating method (solution method). Methods for producing a functional thin film by a gas phase method include a physical method such as a vacuum evaporation method and a sputtering method, and a chemical method such as a CVD method. Examples of the method for producing a functional thin film by a coating method include a spray method, a dipping method, and a screen printing method.

The method for producing a functional thin film by the vapor phase method can obtain a high-performance and high-quality thin film, but it requires a precise control of the atmosphere in a high vacuum system, and has a special problem. However, there is a problem that a complicated heating device or an ion generation accelerating device is required, and the manufacturing cost is inevitably increased because the manufacturing device is complicated and large. Further, the method for producing a functional thin film by the vapor phase method has a problem that it is difficult to increase the area of the thin film or to produce a thin film having a complicated shape.

On the other hand, among the methods for producing a functional thin film by a coating method, those using a spray method have problems such as poor use efficiency of a coating solution and difficulty in controlling film forming conditions. In addition, among the methods for producing a functional thin film using a coating method, those using a dipping method, a screen printing method, and the like have good utilization efficiency of a film forming material and have advantages in mass production and equipment cost, In general, functional thin films obtained by the coating method
There is a problem that the function and quality are inferior to the thin film obtained by the gas phase method.

[0005]

In recent years, as a method of obtaining a thin film of excellent quality by a coating method, a dispersion in which inorganic or organic ultrafine particles are dispersed in an acidic and / or alkaline aqueous solution is applied onto a substrate, A firing method has been proposed. This manufacturing method is advantageous in terms of mass production and equipment costs, but requires a high-temperature baking process during the manufacturing process, which makes it impossible to form a film on a plastic base material. That the uniformity of the obtained thin film is not enough due to the difference in the degree of shrinkage between the film and the coating film, the problem that the performance is still inferior when compared to the thin film obtained by the gas phase method, (For example, several tens of minutes or more), and there is a problem that productivity is poor.

In response to the above problems, the present inventors have already proposed R
_m Si (OR ′) _n (R is an alkyl group having 1 to 10 carbon atoms, or a reactive group such as a vinyl group, a (meth) acryloyl group, an epoxy group, an amide group, a sulfonyl group, a hydroxyl group, and a carboxyl group; Represents an alkyl group having 1 to 10 carbon atoms, and m + n is an integer of 4). An alkoxysilane hydrolysis solution prepared by hydrolyzing a silicon alkoxide represented by A so-called low refraction having a refractive index of 1.38 to 1.46 by forming the organopolysiloxane layer by heating at a low temperature that does not damage the base material, and applying the formed coating layer through a layer. A method for efficiently producing a high-quality functional thin film having a desired rate has been proposed (patent pending).

However, in this method, heating at a relatively low temperature requires a long time (for example, at 100 ° C. for 4 days to 120 ° C.).
(Approximately 1 hour at ℃), which is disadvantageous in equipment and manufacturing cost. Further, the resin base material that can be used as a support base material for the organopolysiloxane layer has also been limited to a base material having a certain degree of heat resistance due to heat treatment. For this reason, for example, excellent optical properties, triacetyl cellulose film, polyvinyl alcohol film, etc.
There is a problem that it cannot be used because it is very weak to heat.

The present invention has been made in view of the above problems, and has as its object to provide a method of manufacturing an optically functional film employing a coating method, and a method of manufacturing an optically functional film obtained by the method. 1.38 refractive index without any process
A so-called organopolysiloxane thin film having a low refractive index of from 1.46 to 1.46 can be formed, mass production is easy, and a method for producing an optical functional film advantageous in terms of equipment cost and production cost, and a method for producing the same are provided. It is an object of the present invention to provide a provided optical functional film.

[0009]

The above object is achieved by the present invention described below.

That is, the optical functional film of the present invention is an optical functional film composed of an organopolysiloxane layer supported directly or via another layer on a substrate, wherein the optical functional film is R _m Si (OR ′) _n Formula (1) (R is an alkyl group having 1 to 10 carbon atoms, or a vinyl group,
A reactive group such as (meth) acryloyl group, epoxy group, amide group, sulfonyl group, hydroxyl group, carboxyl group, R ′
Represents an alkyl group having 1 to 10 carbon atoms, and m + n is an integer of 4.) An alkoxysilane hydrolysis solution prepared by hydrolyzing a silicon alkoxide represented by the following formula: And the coating layer is cured by an active energy ray to form an organopolysiloxane layer.

A preferred embodiment of the optically functional thin film of the present invention is formed on a high-refractive-index layer formed directly on a substrate or via another layer. The refractive index is higher than the refractive index of the organopolysiloxane layer.

The refractive index of the optically functional thin film of the present invention is 1.38 to 1.46. On the other hand, the refractive index of the high refractive index layer in contact with the optically functional thin film is 1.60.
The above is preferable, and a combination of a high refractive index layer and a low refractive index layer having a refractive index in such a range exhibits functions such as antireflection properties, ultraviolet ray blocking properties, and heat ray reflectivity by adopting a desired refractive index. Is done.

Further, the method for producing an optically functional film of the present invention comprises:
A high-refractive-index layer having a higher refractive index than the organopolysiloxane layer described later is formed on the transparent resin substrate directly or via another layer, and then the silicon alkoxide represented by the formula (1) is hydrolyzed. An alkoxysilane hydrolysis solution prepared by decomposition is applied on the high refractive index layer, and the formed application layer is irradiated with active energy rays to cure the application layer to form an organopolysiloxane layer. Features.

According to the present invention, the coating layer formed directly or via another layer on the transparent resin base material is cured into an organopolysiloxane layer by irradiating ultraviolet rays instead of heating. Heat treatment can be omitted. Thereby, in the present invention, the optical functional film of the present invention can be formed even on a substrate having no heat resistance, and is harder than a process requiring a heating step, particularly a low-temperature heating process. The time is short, which is advantageous in terms of mass production and equipment costs.

In the formation of the optical functional film of the present invention, a coating layer formed by applying an alkoxysilane hydrolysis solution prepared by hydrolyzing the silicon alkoxide represented by the above formula (1) is formed by an active energy ray. The change to the organopolysiloxane layer is largely due to the metal oxide contained in other layers or the high refractive index layer. When the adjacent layer in contact with the coating layer contains a metal oxide having an excellent effect of absorbing active energy rays (for example, ultraviolet rays), the metal oxide-containing layer and the coating layer (alkoxysilane hydrolyzate layer) This is because the hardening reaction at the interface with the metal is accelerated. Therefore, the adhesion between the metal oxide-containing layer and the organopolysiloxane layer is improved, and the surface hardness is high.
A thin film of a high quality optical functional film can be obtained.

The optical functional film of the present invention can impart various optical functional characteristics to a transparent resin substrate. For example, the surface of a polarizing plate used for various displays such as word processors, computers and televisions, and liquid crystal display devices. , Sunglass lenses, prescription eyeglass lenses, optical lenses such as viewfinder lenses for cameras, covers for various instruments, window glasses for cars, trains, etc., such as anti-reflection function, ultraviolet ray blocking function, heat ray reflection function, etc. This is useful for the purpose of giving

[0017]

Next, the present invention will be described in more detail with reference to preferred embodiments.

Metal Oxide-Containing Layer In the optical functional film of the present invention, it is desirable that another adjacent layer or a high refractive index layer contains a metal oxide having an excellent ultraviolet absorbing ability. Such a metal oxide may be composed of a single metal species or a composite metal oxide composed of two or more metal species. As the metal oxide, for example, zirconium oxide, titanium oxide, tin oxide, zinc oxide, cerium oxide, antimony oxide, lanthanum oxide, yttrium oxide, aluminum oxide, ITO, ATO, and the like are used.

The metal oxide-containing layer may be a continuous film of a metal oxide or a layer in which metal oxide fine particles are dispersed in a binder. As a method for forming the metal oxide-containing layer, either a gas phase method or a solution method may be used.

In the case of the vapor phase method, a metal oxide film can be formed by a vacuum technique such as an evaporation method, a sputtering method, an ion plating method, and a CVD method.

In the case of a coating method (solution method), for example, a coating liquid in which metal oxide fine particles are dispersed in an organic binder is applied by various coating techniques.
As the organic binder used at this time, it is preferable to use an ionizing radiation-curable resin that does not require a high temperature when the coating film is cured. As the ionizing radiation-curable resin suitable as an organic binder, preferably those having an acrylate-based functional group, for example, a polyester resin having a relatively low molecular weight, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, Spiroacetal resin, polybutadiene resin, polythiolpolyene resin, oligomer or prepolymer such as (meth) acrylate of polyfunctional compound such as polyhydric alcohol, and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene as reactive diluent , Methyl styrene,
Monofunctional monomers such as N-vinylpyrrolidone and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentane Erythritol tri (meth) acrylate,
Dipentaerythritol hexa (meth) acrylate,
Those containing relatively large amounts of 1,6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate and the like can be used.

Further, in order to convert the above ionizing radiation-curable resin into an ultraviolet-curable resin, an acetophenone, a benzophenone, a Michler benzoyl benzoate, an α-amyl oxime ester, a tetramethyl Thiuram monosulfide, thioxanthones, and n-butylamine, triethylamine, tri-n-butylphosphine, and the like can be mixed and used as a photosensitizer.

The curing of the metal oxide fine particle-containing layer is performed by:
A usual method of curing an ionizing radiation-curable resin, that is, a method of curing by irradiation with an electron beam or ultraviolet light can be used. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as Cockloft-Walton type, Bande graph type, Resonant transformation type, Insulating core transformer type, Linear type, Dynamitron type and High frequency type. Preferably, an electron beam or the like having an energy of 100 to 300 KeV is used.
Ultraviolet rays emitted from light rays such as a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.

As a coating solution for forming the metal oxide-containing layer by the solution method, a metal oxide precursor solution may be used without using an organic binder. In that case, a metal alkoxide, a metal salt, or the like dissolved in a solvent is preferably used. At the time of coating, the metal alkoxide, metal salt and the like may or may not be hydrolyzed.

In order to increase the mechanical strength of the optically functional film, it is preferable to provide a hard coat layer between the resin substrate and the metal oxide containing layer. Alternatively, a metal oxide-containing hard coat layer in which the metal oxide-containing layer has a hard coat property may be provided between the resin substrate and the organopolysiloxane layer.

As the hard coat material, the same organic resin as the binder of the metal oxide fine particle dispersion is preferably used.

Alkoxysilane Hydrolysis Solution Specific compounds of the silicon alkoxide represented by the formula (1) used in the present invention include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n- Propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-
Butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane,
Dimethylmethoxysilane, dimethyldimethoxysilane,
Dimethylethoxysilane, dimethyldiethoxysilane,
Dimethylpropoxysilane, dimethylbutoxysilane,
Methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, 3-
(-2-aminoethylaminopropyl) trimethoxysilane and the like.

The hydrolysis of the silicon alkoxide is performed by dissolving the silicon alkoxide in a suitable solvent. As the solvent used, for example, methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate, alcohols such as ethyl acetate, ketones, esters, halogenated hydrocarbons, toluene, aromatic hydrocarbons such as xylene, Alternatively, a mixture thereof may be mentioned.

The above-mentioned silicon alkoxide is used in the above-mentioned solvent,
The alkoxide is dissolved in such a manner that the concentration of the alkoxide hydrolyzed solution produced as a result of 100% hydrolysis and condensation is 0.05% or more, preferably 0.1 to 30% by weight in terms of solid content. If the concentration of the alkoxysilane hydrolysis solution is less than 0.05% by weight, the functional film formed cannot exhibit desired properties sufficiently, while if it exceeds 30% by weight, it becomes difficult to form a transparent homogeneous film. . In the present invention, an organic or inorganic binder can be used in combination within the concentration range of the alkoxysilane hydrolysis solution.

To a solution of the above silicon alkoxide in the above solvent, water was added in an amount not less than the amount required for hydrolysis.
At a temperature of ~ 35 ° C, preferably 22-28 ° C, 1-12
The stirring is carried out for a time, preferably for 2 to 6 hours.

In the above-mentioned hydrolysis, it is preferable to use a catalyst, such as hydrochloric acid, nitric acid, or the like.
Acids such as sulfuric acid or acetic acid are preferably used. These acids are about 0.001 to 20.0 N, preferably 0.005 to
It is used as an aqueous solution of about 5.0N. The water in the aqueous catalyst solution can be used as water for hydrolysis. That is, an aqueous solution of a catalyst is added to a silicon alkoxide solution and hydrolysis is performed to obtain an alkoxysilane hydrolysis solution.

In the above alkoxysilane hydrolysis solution,
Various additives can be added. The most important additives include curing agents that promote film formation, and examples of these curing agents include organic acid solutions of organic acid metal salts such as sodium acetate and lithium acetate, such as acetic acid and formic acid. The concentration of the organic acid solvent solution is about 0.01 to 0.1% by weight, and the amount added to the alkoxysilane hydrolysis solution is based on 100 parts by weight of the solids present in the alkoxysilane hydrolysis solution. About 0.
The range is preferably about 1 to 1 part by weight.

Further, when the finally obtained organopolysiloxane layer is used for purposes such as an antireflection film, a heat ray reflection film and a scattering film, it is necessary to adjust the refractive index thereof. A fluorinated organic silicon compound can be added to reduce the refractive index, and an organic silicon compound can be added to increase the refractive index.

Specifically, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, alkyl trialkoxysilane, Colcoat 40 (trade name, manufactured by Colcoat), MS51 (trade name, manufactured by Mitsubishi Chemical), HS56 (trade name: manufactured by Mitsubishi Chemical Corporation),
Organosilicon compounds such as Snowtex (trade name: manufactured by Nissan Chemical); Zaflon FC-110, 220, 250 (trade name: manufactured by Toa Gosei Chemical), sexual coat A-402B
(Trade name: manufactured by Central Glass), fluorinated compounds such as heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, trifluoropropyltrimethoxysilane; triethyl borate, trimethyl borate, tripropyl borate, tributyl borate, etc. Of boron-based compounds.

These additives may be added at the time of hydrolysis of the silicon alkoxide, or may be added after the hydrolysis.
By using these additives, a more uniform and transparent solution is obtained by reacting with the silanol group during or after the hydrolysis of the silicon alkoxide, and the refractive index of the formed organopolysiloxane layer is within a certain range. Can be changed.

The hydrolyzed alkoxysilane solution obtained as described above is a colorless and transparent liquid, a stable solution having a pot life of about 1 month or more, has good leakage to the base material, It is reasonably good and its molecular weight is usually 3
It is about 100 to 100,000.

Substrate As the substrate on which the optical functional film of the present invention is supported directly or via another layer, a transparent resin substrate is suitable for optical use. Such a transparent resin substrate may be, for example, a plate-like material such as an acrylic plate or a film-like material such as a polyethylene terephthalate film.
Since the optical functional film of the present invention does not require a heating step in its manufacturing process, a plastic film having no heat resistance can be used, and the present invention has many types of base films that can be used. Therefore, conventionally, as a substrate film of an optical functional film, generally used triacetyl cellulose film, polyvinyl alcohol film, and the like have particularly low heat resistance, and an organopolysiloxane layer is formed on the film by a coating method. Although it was impossible, the present invention can use even such a resin film.

As a plastic film usable in the present invention, a polyethylene terephthalate film,
Polyethylene film, nylon film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, trimethylpentene film, polyetherketone film , (Meth) acrylonitrile film, polyvinyl alcohol film, triacetyl cellulose film and the like. In particular, a polyethylene terephthalate film, a polyvinyl alcohol film, and a triacetyl cellulose film are suitably used for optical applications. The thickness of the transparent resin substrate film is usually 5μ.
Those having a size of about m to 1000 μm are suitably used.

Organopolysiloxane layer (optical function)
The form formed present invention the membrane), the relative alkoxysilane hydrolysis solution surface of the transparent resin substrate and is coated with a coating method to form a coating layer, that then the coating layer is an active energy ray irradiation treatment Thereby, an organopolysiloxane layer is formed.

As a method for applying the above-mentioned alkoxysilane hydrolysis solution to a resin substrate, there are spin coating, dipping, bar coating, die coating, slide coating, and the like.
Examples include a spray method, a roll coating method, a meniscus coating method, a flexographic printing method, a screen printing method, and a bead coating method.

For forming the organopolysiloxane layer, irradiation with active energy rays is effectively used. Active energy rays include electron beams and electromagnetic waves such as γ-rays, X-rays,
Ultraviolet light, visible light, infrared light and the like can be used, but ultraviolet light is preferably used.

As the ultraviolet rays, ultraviolet rays emitted from a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, an excimer lamp, and an excimer laser are used. The wavelength range is
It is preferably one corresponding to the absorption of metal oxides,
For example, in the case of zirconia, the wavelength is shorter than about 400 nm, and in the case of titania, the wavelength is shorter than 420 nm. The total dose of active energy rays is 50 mJ
/ Cm ² or more, preferably 100 to 800 mJ / cm ²
Is preferable.

Generally, ultraviolet irradiation is performed in the air.
In the present invention, it is preferable to perform in a sufficient nitrogen atmosphere,
By performing the treatment in a nitrogen atmosphere, the formation, polymerization, and condensation of Si—O—Si bonds are promoted, and a more uniform and high-quality organopolysiloxane layer can be formed.

As described above, in the method for producing an optical functional film of the present invention, an optical functional film having a desired function can be obtained by selecting a coating material to be used. The optical functional film obtained by the present invention can be used as a low refractive index layer in a multilayer antireflection film.

The thickness of the optical functional film of the present invention is 0.03 to 0.03.
The range of 3 μm is preferable for exhibiting optical characteristics.

[0046]

The optical functional film of the present invention will be described below with reference to examples.

Example 1 Preparation of Hydrolysis Solution of Alkoxysilanes Assuming that methyltriethoxysilane (MTEOS) was ideally completely hydrolyzed and condensed, the solid content concentration was 6% by weight. MTEOS was dissolved in methyl ethyl ketone as a solvent, and the mixture was stirred for 30 minutes until the liquid temperature was stabilized at 25 ° C. (Solution A). Hydrochloric acid having a concentration of 0.005N, which is a catalyst, was added to Solution A in an equimolar amount to the alkoxy group of MTEOS, and hydrolysis was performed at 25 ° C. for 3 hours (B
liquid). A mixture of sodium acetate and acetic acid as a curing agent was added to the solution B, and the mixture was stirred at 25 ° C. for 1 hour to obtain an alkoxysilane hydrolysis solution. Solids concentration 1.5
The coating solution was diluted with isopropyl alcohol to give a coating solution by weight.

Formation of Hard Coat Layer PET film having a smooth surface (A-4300: trade name,
1 hard coat resin (X-12-2400: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) on Toyobo, 100 μm thick
Coating is performed by gravure reverse coating so as to be 0 μm / dry, and an electron beam is applied at an acceleration voltage of 175 KeV and 5 Mra.
Irradiation d cured the coating to form a hard coat layer.

Formation of Layer Containing Metal Oxide Fine Particles On the hard coat layer obtained in the above step, a dispersion of zirconia fine particles (No. 1275A: trade name, manufactured by Sumitomo Osaka Cement) having a refractive index of 1.9 was applied. 0.3 μm / dr
y, and accelerate the electron beam with an accelerating voltage of 175 KeV
The coating was cured by irradiating with 5 Mrad to form a zirconia fine particle-containing layer.

Formation of Organopolysiloxane Layer On the zirconia fine particle-containing layer obtained in the above step,
0.1 μm /
It was applied with a dry film thickness. This coating film was irradiated with a single irradiation dose of 160 mJ / cm ^{2 at} 240 W using an ultraviolet irradiation device.
Irradiation was performed four times, and the total irradiation amount was 640 mJ / cm ²
Thus, an organopolysiloxane layer was formed.

Evaluation of Characteristics of Organopolysiloxane Layer The refractive index of this organopolysiloxane layer was 1.42. As for the surface hardness, a scratch test was performed using a steel wool of # 0000, but the coating film was not damaged even after reciprocating 20 times with a load of 200 g. In addition, the adhesiveness by the tape peeling test was 100 (100)% in both cases, and the adhesiveness to the zirconia fine particle-containing layer was also good.

Example 2 Preparation of Alkoxysilane Hydrolysis Solution An alkoxysilane hydrolysis solution was prepared in the same manner as in Example 1.

Formation of Hard Coat Layer Containing Metal Particles A PET film (A-4350: trade name, manufactured by Toyobo) having a thickness of 100 μm was prepared as a transparent base film. On the other hand, zirconia fine particles having a refractive index of 1.9 (No. 1275)
A: A dispersion liquid of trade name, manufactured by Sumitomo Osaka Cement) and an ionizing radiation curable resin (X-12-2400-6: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed at a weight ratio of 2: 1. The obtained resin composition was applied on a PET film by gravure reverse coating so as to have a thickness of 7 μm / dry, and the solvent was removed by drying. After that, the electron beam was 5M at 175 KeV.
The coating film was cured by rad irradiation to form a zirconia fine particle-containing hard coat layer.

Formation of Organopolysiloxane Layer On the hard coat layer containing zirconia fine particles obtained as described above, an alkoxysilane hydrolysis solution of 0.1 μm was applied.
/ Dry. Using a UV irradiation device, the irradiation amount of this coating film at 240 W was increased by 160 mJ / cm.
Irradiation was performed 4 times as ² and the total irradiation amount was 640 mJ / cm.
^{This was} designated as ² , and an organopolysiloxane layer was formed.

Evaluation of Characteristics of Organopolysiloxane Layer The refractive index of this organopolysiloxane layer was 1.42. As for the surface hardness, a scratch test was performed using a steel wool of # 0000, but the coating film was not damaged even after reciprocating 20 times with a load of 200 g. In addition, the adhesiveness by the tape peeling test was 100 (100)% in both cases, and the adhesiveness to the zirconia fine particle-containing layer was also good.

Example 3 Preparation of Alkoxysilane Hydrolysis Solution An alkoxysilane hydrolysis solution was prepared in the same manner as in Example 1.

Formation of Metal Oxide-Containing Fine Particle Layer PET film having a smooth surface (A-4300: trade name,
A dispersion of zirconia fine particles (No. 1275A: trade name, manufactured by Sumitomo Osaka Cement) is applied to a thickness of 0.3 μm / dry on Toyobo, thickness 100 μm), and an electron beam is applied at an acceleration voltage of 175 KeV at 5 Mrad. The coating was cured by irradiation to form a layer containing zirconia fine particles.

Formation of Organopolysiloxane Layer On the zirconia fine particle-containing layer obtained above, the above-mentioned alkoxysilane hydrolysis solution was applied at a concentration of 0.1 μm / dry.
Was applied with a film thickness of This coating film was irradiated four times at 240 W with an irradiation amount of 160 mJ / cm ² using an ultraviolet irradiation device, and the total irradiation amount was 640 mJ / cm ² ,
An organopolysiloxane layer was formed.

Evaluation of Characteristics of Organopolysiloxane Layer The refractive index of this organopolysiloxane layer was 1.42. As for the surface hardness, a scratch test was performed using a steel wool of # 0000, but the coating film was not damaged even after reciprocating 20 times with a load of 200 g. In addition, the adhesiveness by the tape peeling test was 100 (100)% in both cases, and the adhesiveness to the zirconia fine particle-containing layer was also good.

Example 4 Preparation of Alkoxysilane Hydrolysis Solution An alkoxysilane hydrolysis solution was prepared in the same manner as in Example 1.

Formation of Hard Coat Layer Triacetyl cellulose film having a smooth surface (abbreviation:
Hard coat resin (PET-D) on TAC film
31: trade name, manufactured by Nippon Kayaku Co., Ltd.) by gravure reverse coating so as to have a concentration of 5 μm / dry, and irradiating the coating film three times with 240 W of ultraviolet light at a single irradiation amount of 30 mJ / cm ² The total irradiation amount was 90 mJ / cm ² , and a hard coat layer was formed.

Formation of Layer Containing Metal Oxide Fine Particles On the hard coat layer obtained in the above step, a dispersion of zirconia fine particles (No. 1275A: trade name, manufactured by Sumitomo Osaka Cement) was adjusted to 0.3 μm / dry. And apply a single dose of 30 mJ / cm with UV 240 W
² as carried out twice irradiation, and curing the coating film was irradiated with a total dose 60 mJ / cm ^2, to form a zirconia fine particle-containing layer.

Formation of Organopolysiloxane Layer On the zirconia fine particle-containing layer obtained in the above step,
0.1 μm / dr of the alkoxysilane hydrolysis solution
It was applied with a film thickness of y. This coating film was irradiated 6 times with an ultraviolet irradiation device at 240 W at an irradiation amount of 30 mJ / cm ² , and the total irradiation amount was 180 mJ / cm ² .
An organopolysiloxane layer was formed.

Evaluation of Characteristics of Organopolysiloxane Layer The refractive index of this organopolysiloxane layer was 1.42. As for the surface hardness, a scratch test was performed using a steel wool of # 0000, but the coating film was not damaged even after reciprocating 20 times with a load of 200 g. In addition, the adhesiveness by the tape peeling test was 100 (100)% in both cases, and the adhesiveness to the zirconia fine particle-containing layer was also good.

Example 5 Preparation of Alkoxysilane Hydrolysis Solution An alkoxysilane hydrolysis solution was prepared in the same manner as in Example 1.

Formation of Hard Coat Layer Containing Metal Oxide Fine Particles Triacetyl cellulose film having a smooth surface (abbreviation:
TAC film). On the other hand, zirconia fine particles having a refractive index of 1.9 (No. 1275A: trade name, manufactured by Sumitomo Osaka Cement) and ionizing radiation-curable resin (X-12-24)
00-6: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) in a weight ratio of 2: 1.
Was mixed. The obtained resin composition was applied on a PET film by gravure reverse coating so as to have a film thickness of 7 μm / dry, and this coating film was irradiated with UV light at 240 W for 1 hour.
Irradiation is performed three times with the irradiation amount of 30 mJ / cm ² ,
The total irradiation amount was 90 mJ / cm ^2, and a hard coat layer containing zirconia fine particles was formed.

Formation of Organopolysiloxane Layer On the zirconia fine particle-containing hard coat layer obtained in the above step, an alkoxysilane hydrolysis solution of 0.1 g was added.
It was applied at a film thickness of 1 μm / dry. This coating film was irradiated with a single irradiation dose of 30 mJ / 240 W at 240 W using an ultraviolet irradiation device.
Irradiation was performed 6 times with a total irradiation amount of 180 mJ / cm ^2.
cm ² to form an organopolysiloxane layer.

Evaluation of Characteristics of Organopolysiloxane Layer The refractive index of this organopolysiloxane layer was 1.42. As for the surface hardness, a scratch test was performed using a steel wool of # 0000, but the coating film was not damaged even after reciprocating 20 times with a load of 200 g. In addition, the adhesiveness by the tape peeling test was 100 (100)% in both cases, and the adhesiveness to the zirconia fine particle-containing layer was also good.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the zirconia fine particle-containing layer was not formed on the hard coat layer.
An organopolysiloxane layer was formed under the same conditions as described above. The refractive index of this organopolysiloxane layer was 1.42.
Met. Also, due to the low surface hardness, scratching occurred in a scratch test with steel wool. further,
The adhesiveness to the hard coat layer was low, and it was not a high-performance optical thin film.

Comparative Example 2 An organopolysiloxane layer was formed under the same conditions as in Example 2 except that the zirconia fine particles were not contained in the hard coat layer. The refractive index of this organopolysiloxane layer was 1.42. Also, due to the low surface hardness, scratching occurred in a scratch test with steel wool. Furthermore, the adhesiveness with the hard coat layer was low, and it was not a high-performance optical thin film.

Comparative Example 3 An organopolysiloxane layer was formed under the same conditions as in Example 3 except that the zirconia fine particle-containing layer was not formed. The refractive index of this organopolysiloxane layer was 1.42. Also, due to the low surface hardness, scratching occurred in a scratch test with steel wool. Furthermore, the adhesiveness with a PET film was low, and it was not a highly functional optical thin film.

Comparative Example 4 The procedure of Example 4 was repeated except that the zirconia fine particle-containing layer was not formed on the hard coat layer.
An organopolysiloxane layer was formed under the same conditions as described above. The refractive index of this organopolysiloxane layer was 1.42.
Met. Also, due to the low surface hardness, scratching occurred in a scratch test with steel wool. further,
The adhesiveness to the hard coat layer was low, and it was not a high-performance optical thin film.

Comparative Example 5 An organopolysiloxane layer was formed under the same conditions as in Example 5 except that zirconia fine particles were not contained in the hard coat layer. The refractive index of this organopolysiloxane layer was 1.42. Also, due to the low surface hardness, scratching occurred in a scratch test with steel wool. Furthermore, the adhesiveness with the hard coat layer was low, and it was not a high-performance optical thin film.

[0074]

As described above, according to the present invention, R _m is used as a starting material.
Si (OR ′) _n (R is an alkyl group having 1 to 10 carbon atoms,
Or a vinyl group, a (meth) acryloyl group, an epoxy group,
An amide group, a sulfonyl group, a hydroxyl group, a reactive group such as a carboxyl group, R ′ represents an alkyl group having 1 to 10 carbon atoms,
(m + n is an integer of 4) by using an alkoxysilane hydrolysis solution obtained by hydrolyzing a silicon alkoxide represented by the formula (1), so that a so-called refractive index of 1.38 to 1.46 can be obtained without a heating step. An optical functional film that can be used for optical applications of an organopolysiloxane thin film having a low refractive index can be obtained, and the method for producing an optical functional film of the present invention can be performed at a low temperature and in a short time by irradiating active energy rays.
An optically high-functional organopolysiloxane layer is obtained,
It is easy to mass produce, and is advantageous in terms of equipment costs and manufacturing costs.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 83:04 (72) Inventor Toshio Yoshiwara 1-1-1 Ichigayakacho, Shinjuku-ku, Tokyo Large Within Nippon Printing Co., Ltd. (72) Inventor Noboru Kunimine 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo F-term within Nippon Printing Co., Ltd. 2H048 CA05 CA13 2K009 AA02 BB24 CC42 DD03 DD04 4F006 AA02 AA19 AB39 AB74 DA01 DA04 EA03 4J038 DL031 GA01 GA03 GA06 GA07 GA09 GA13 HA216 JC32 NA19 PA07 PA17 PC08

Claims (12)

[Claims] 1. An optically functional film supported on a substrate directly or via another layer, wherein R _m Si (OR ′) _n (R is an alkyl group having 1 to 10 carbon atoms, or Vinyl group,
A reactive group such as (meth) acryloyl group, epoxy group, amide group, sulfonyl group, hydroxyl group, carboxyl group, R ′
Represents an alkyl group having 1 to 10 carbon atoms, and m + n is an integer of 4.) An alkoxysilane hydrolysis solution prepared by hydrolyzing a silicon alkoxide represented by An optical functional film, wherein the coating layer is cured by an active energy ray to form an organopolysiloxane layer. 2. The optically functional film is formed on a high refractive index layer formed directly or via another layer on a base material, and the refractive index of the high refractive index layer is organo. 2. The optical functional film according to claim 1, wherein the refractive index is higher than the refractive index of the polysiloxane layer. 3. The optical functional film according to claim 1, wherein the high refractive index layer has a refractive index of 1.60 or more. 4. The optical functional film according to claim 1, wherein the thickness of the organopolysiloxane layer is in the range of 0.03 to 3 μm. 5. The optical functionality according to claim 1, wherein the other layer or the high-refractive-index layer contains a metal oxide having an excellent ultraviolet absorbing ability. film. 6. The method according to claim 1, wherein the high refractive index layer comprises zirconium oxide,
2. The optical function according to claim 1, wherein at least one metal oxide selected from titanium oxide, tin oxide, ITO, zinc oxide and cerium oxide is formed by a solution method or a gas phase method. Membrane. 7. The optical functional film according to claim 1, wherein the refractive index of the organopolysiloxane layer is in the range of 1.38 to 1.46. 8. A high-refractive-index layer having a higher refractive index than an organopolysiloxane layer to be described later is formed directly or via another layer on a transparent resin substrate, and then R _m Si (OR ′) _n (R is an alkyl group having 1 to 10 carbon atoms, or a vinyl group,
A reactive group such as (meth) acryloyl group, epoxy group, amide group, sulfonyl group, hydroxyl group, carboxyl group, R ′
Represents an alkyl group having 1 to 10 carbon atoms, and m + n is an integer of 4.) A hydrolyzed alkoxysilane solution prepared by hydrolyzing a silicon alkoxide represented by Irradiating the formed coating layer with an active energy ray to cure the coating layer to form an organopolysiloxane layer. 9. The method for producing an optically functional film according to claim 8, wherein the other layer or the high-refractive-index layer contains a metal oxide having an excellent ultraviolet absorbing ability. 10. The method according to claim 8, wherein the active energy rays are ultraviolet rays. 11. The irradiation amount of the ultraviolet ray is 50 mJ / cm.
9. The method for producing an optically functional film according to claim 8, wherein the number is ² or more. 12. The method for producing an optically functional film according to claim 8, wherein the transparent resin substrate is a triacetyl cellulose film or a polyvinyl alcohol film.