JPH05237442A - Production of membrane - Google Patents

Abstract

(57) [Abstract] [Purpose] A method for producing a thin film, in which a thin film can be freely formed on a desired film-forming substance simply by irradiating micelle solutions or dispersion liquids of various film-forming substances with light. It is to develop. [Structure] Various dyes and pigments are dispersed or solubilized in an aqueous medium using a surfactant composed of a ferrocene derivative, and a specific concentration of a photooxidation catalyst and a photooxidation catalyst regenerator are mixed at a constant mixing ratio. After adjusting the pH of the added micelle solution or dispersion to 5 or less,
By inserting the film-forming substance, by irradiating the contact surface of the micelle solution or dispersion and the film-forming substance with light,
A method of forming a thin film of the inorganic material or the hydrophobic organic material on a non-exposed portion of the film-forming material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a thin film,
More specifically, the present invention relates to a method for producing a thin film, which allows a thin film to be freely formed on a desired film-forming substance simply by irradiating a micelle solution or dispersion liquid of various film-forming substances with light.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Thin film manufacturing methods include vapor deposition, spin coating, CV
D method, sputtering method, LB film method, dipping method, electrodeposition method, micelle electrolysis method, printing method, dispersion method, dyeing method and the like are known. Among them, the production of a thin film by the micelle electrolysis method has good accuracy and is expected to be industrially used.
However, in the micelle electrolysis method and the electrodeposition method, since the film is formed using electricity, the material to be film-formed needs to be a conductor. In the case of a color filter, ITO (Indium Tin Oxid)
Since e) is patterned by photolithography, an exposure step and an etching step are required, and
It was difficult to obtain a pattern accuracy with a gap of 5 μm or less due to the limitation of etching conditions. Therefore, the inventors of the present invention have conducted earnest studies to develop a completely new thin film manufacturing method capable of freely forming a thin film without using electricity or performing an etching process.

[0003]

As a result, a micellar solution or dispersion containing various film-forming substances and having a specific concentration of a photooxidation catalyst and a photooxidation catalyst regenerating substance added at a mixing ratio within a certain range. It was found that the object can be achieved by adjusting the pH of the liquid to 5 or less, inserting a film-forming substance, and irradiating the contact surface between the liquid and the film-forming substance with light. The present invention has been completed based on such findings.

That is, an inorganic substance or a hydrophobic organic substance is dispersed or solubilized in an aqueous medium using a surfactant composed of a ferrocene derivative, and 1 to 100
The pH of the micelle solution or dispersion obtained by adding the photooxidation catalyst in the mM range and the regenerated substance of the photooxidation catalyst in the range of 1 to 100 mM in the range of 1: 5 to 5: 1 is adjusted to 5 or less. After that, by inserting the film-forming substance, by irradiating the contact surface of the micelle solution or dispersion and the film-forming substance with light, the inorganic substance or the non-exposed portion on the non-exposed portion of the film-forming substance. The present invention provides a method for manufacturing a thin film, which comprises forming a thin film of a hydrophobic organic substance.

There are various film forming materials (thin film materials) used in the present invention, and they can be broadly classified into inorganic materials and hydrophobic organic materials. Here, there are various kinds of hydrophobic organic substances, for example, phthalocyanine, metal complexes of phthalocyanine and derivatives thereof, naphthalocyanine, metal complexes of naphthalocyanine and derivatives thereof, porphyrin, metal complexes of porphyrin and these Derivatives, perylene, derivatives of perylene, quinacridone, isoindolinone, disazo, dioxazine, viologen, sudan and color filter pigments such as these derivatives and organic dyes, including 1,
Electrochromic materials such as 1'-diheptyl-4,4'-bipyridinium dibromide, 1,1'-didodecyl-4,4'-bipyridinium dibromide, 6-
Nitro-1,3,3-trimethylspiro- (2'H-
Photosensitive material (photochromic material) such as 1'-benzopyran-2,2'-indoline) (commonly called spiropyran)
And optical sensor materials, liquid crystal display dyes such as p-azoxyanisole, and "Color Chemical Encyclopedia" CMC Co., Ltd., No. 542-71, published on March 28, 1988.
Electronic dyes, recording dyes, environmental chromism dyes, photographic dyes, energy dyes, biomedical dyes, food and cosmetic dyes, listed on page 7.
Examples include dyes, pigments, and hydrophobic compounds among special coloring pigments. Further, an organic conductive material such as a 1: 1 complex of 7,7,8,8-tetracyanoquinone dimethane (TCNQ) and tetrathiafulvalene (TTF), a gas sensor material, and a photocurable material such as pentaerythritol diacrylate. Examples thereof include paints, insulating materials such as stearic acid, diazo type photosensitive materials such as 1-phenylazo-2-naphthol, paints, and the like. Furthermore, water-insoluble polymers such as polycarbonate, polystyrene, polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (PPO), polyacrylonitrile (PAN).
Polymers such as polyphenylene, polypyrrole, polyaniline, polythiophene, acetyl cellulose, polyvinyl acetate, polyvinyl butyral, and various other polymers (polyvinyl pyridine, etc.)
Alternatively, a copolymer (such as a copolymer of methyl methacrylate and methacrylic acid) can be used.

On the other hand, there are various kinds of inorganic substances such as inorganic oxides and inorganic sulfides. For example, TiO ₂ ,
_{C, CdS, FeO 3, Y} 2 O 3 -ZrO 2, Zr
O ₂ , Al ₂ O ₃ , CuS, ZnS, TeO ₂ , LiNb
O ₃ , Si ₃ N ₄ , SrCeO ₃ , WO ₃ , PLZT and various superconducting oxides can be used. Of these various inorganic or hydrophobic organic substances, red,
The pigments or dyes having the spectral characteristics of the three primary colors of green and blue, that is, the hydrophobic pigments of red, green and blue, can be used for manufacturing color filters. Examples of red dyes include perylene pigments, lake pigments, azo pigments, quinacridone pigments, anthraquinone pigments, and anthracene pigments.
Lake pigments (Ca, Ba, Sr, Mn), quinacridone, naphthol AS, shicomin pigments, anthraquinone (Sudan I,
II, III, R), disazo, benzopyran, cadmium sulfide-based pigments, Fe (III) oxide-based pigments and the like, of which the perylene pigments and lake pigments are preferred. As the green pigment, there are halogen polysubstituted phthalocyanine pigments, halogen polysubstituted copper phthalocyanine pigments, triphenylmethane basic dyes and the like, for example, chloropolysubstituted phthalocyanines, copper complexes thereof or barium-triphenylmethane dyes. There are copper phthalocyanine-based pigments, indanthrone-based pigments, indophenol-based pigments, cyanine-based pigments, and the like as blue dyes. There are phthalocyanine metal complexes such as iron phthalocyanine and cobalt phthalocyanine, phthalocyanine, merocyanine or indophenol blue. Further, a yellow pigment for adjusting chromaticity includes a disazo pigment and an isoindolinone pigment, and a purple pigment includes a dioxazine pigment.

Among the above substances, phthalocyanine metal complexes (copper complex, chloroaluminum complex, chloroindium vanadate complex, indium complex, etc.),
Perylene pigments, diazo pigments, cadmium sulfide pigments and the like act as charge generating substances and are therefore effective as materials for manufacturing electrophotographic photoreceptors. The shape and size of these inorganic substances or hydrophobic organic substances are not particularly limited, but the particle size is preferably 10 μm.
The following powders are used.

Next, in the present invention, various aqueous media such as water, a mixed solution of water and alcohol, a mixed solution of water and acetone can be used as the aqueous medium for forming the thin film.

The surfactant used in the method of the present invention is a surfactant containing a ferrocene derivative as an active ingredient, and there are various types such as nonionic, cationic and anionic. Specifically, JP-A-63-24329
No. 8, an ammonium-type ferrocene derivative, an ether-type ferrocene derivative or an ester-type ferrocene derivative as shown in International Publication WO 89/01939, as disclosed in JP-A-1-226894. Pyridinium type ferrocene derivative, and further, JP-A-2-88387 and JP-A-1-45370.
No. 2-96585 and No. 2-250892.
There may be mentioned various ferrocene derivatives as disclosed in Japanese Patent Publication No.

In the method of the present invention, it is necessary to use a photooxidation catalyst and a photooxidation catalyst regenerator together. In addition, the concentration of the photooxidation catalyst and its regenerated substance in the micelle solution or dispersion must both be selected within the range of 1 to 100 mM, and the mixing ratio of the two must be determined within the range of 1: 5 to 5: 1. Is. Here, if the concentration is less than 1 mM, the photo-oxidation reaction and regeneration of the catalyst do not proceed sufficiently, and if it exceeds 100 mM, these catalysts and regenerated substances are mixed in the formed thin film and the performance of the thin film is reduced. May cause a decline.
As the photo-oxidation catalyst, various ones can be used, but usually a ruthenium complex or the like is preferably used. As the photooxidation catalyst regenerating substance, various substances can be used as long as they can regenerate the deteriorated photooxidation catalyst, but a cobalt complex is usually preferably used.

In the method of the present invention, the above-mentioned surfactant and inorganic substance and / or hydrophobic organic substance are first put in an aqueous medium, and a mechanical homogenizer, an ultrasonic homogenizer, a pearl mill, a sand mill, a stirrer, a triple roll mill, etc. Stir well with. By this operation, the inorganic substance or the hydrophobic organic substance is uniformly dispersed or solubilized in the aqueous medium by the action of the surfactant, and becomes a dispersion liquid or an aqueous solution (micelle solution). The above-mentioned photo-oxidation catalyst and its regenerated substance may be added to an aqueous medium in advance and stirred together with the inorganic substance or the hydrophobic organic substance, or after stirring to prepare a dispersion liquid or a micelle solution, You may add. The concentration of the surfactant at this time is not particularly limited, but usually, the surfactant including the ferrocene derivative is used at a concentration equal to or higher than the limit micelle concentration, preferably 10 μM to 10 μM.
Select in the range of 0 mM. The concentration of the inorganic substance or the hydrophobic organic substance is not particularly limited, but usually 1 to
It may be set in the range of 10 mM. In the present invention, an appropriate amount of a supporting salt such as LiBr or Na ₂ SO ₄ can be added if necessary.

In the method of the present invention, it is necessary to adjust the pH of the micelle solution or dispersion thus obtained to 5 or less using a mineral acid such as hydrochloric acid or an organic acid. When the pH of the micelle solution or dispersion exceeds 5, the photooxidation reaction does not proceed smoothly and the object of the present invention cannot be achieved. In the present invention, a mineral acid or an organic acid may be added to an aqueous medium in advance to adjust the pH to 5 or less, or may be added after preparing a micelle solution or a dispersion liquid. ..

In the method of the present invention, the substance to be formed is inserted into the micelle solution or dispersion whose pH is adjusted to 5 or less as described above, and the contact surface between the micelle solution or dispersion and the substance to be formed is contacted. Irradiate light on. As the film-forming substance used here, various substances can be applied and may be either conductive or insulating. For example, molded products of various metals, alloys, inorganic substances, plastics, soda lime glass, white glazing, non-alkali glass (made by Corning Incorporated:
7059, manufactured by HOYA: NA45), low expansion glass,
Examples thereof include glass such as quartz glass. In the present invention, it is desirable that these film-forming substances be subjected to treatments such as polishing, washing and drying to clean the surface and then be used.

According to the method of the present invention, the micelle solution or dispersion in which the film-forming substance is inserted, and particularly the contact surface between the film-forming substance and the micelle solution or dispersion, is irradiated with light. Irradiation light is not particularly limited as long as it has a wavelength that can be absorbed by an inorganic substance or a hydrophobic organic substance in the micelle solution or dispersion, or can excite the added photooxidation catalyst, and various light can be applied. it can. Specifically, 2
It is possible to irradiate a high pressure mercury lamp of 20 to 5000 mJ / cm ² of kW. If the light irradiation is performed on the film-forming substance through an appropriate exposure mask, the inorganic substance or the hydrophobic organic substance in the micelle solution or the dispersion liquid becomes a thin film on the non-exposed portion on the film-forming substance. In a uniform pattern, and as a result, a patterned thin film corresponding to the mask pattern is formed. The thin film formed by such light irradiation is preferably subjected to baking (baking), pure water cleaning, electrolytic cleaning or the like, if necessary.

[0015]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Example 1 2 m of a ferrocene derivative micelle agent FPEG represented by the following formula (I) (manufactured by Dojindo Co., Ltd.) was added to 1 liter of pure water.
7 mM of M and phthalocyanine was added, and [Ru (bp
y) ₃ ] Cl ₂ (where bpy represents a bipyridyl group) is 10 mM, and [Co (NH ₃ ) ₅ Cl] Cl ₂ is 1
Add 100 cc of 0 mM and 1N HCl, pH = 1.
No. 8 and dispersed by an ultrasonic homogenizer for 30 minutes to prepare a micelle dispersion, and then put the micelle dispersion in the cell shown in FIG. 1 to form an ITO film having an ITO substrate (blue) with a surface resistance of 10 Ω / cm ^2. A plate glass (thickness: 1.1 mm) was fixed to the cell so that air bubbles did not enter. In advance, an extraction electrode was installed on the ITO substrate, a proximity gap of 70 μm was opened on the back surface (upper surface) of the ITO substrate, and from the back surface (upper surface) opposite to the ITO surface, the xenon lamp of the optical system shown in FIG. The mask was exposed. Mask is Figure 1
The one shown in was used. After that, the substrate removed from the cell was washed, drained with a spin dryer, and baked in an oven at 180 ° C. for 1 hour to obtain a thin film on a non-exposed portion shielded from light by a mask.

[0016]

[Chemical 1]

[0017]

[Chemical 2]

Example 2 The same operation as in Example 1 was carried out except that the irradiation time of the xenon lamp was arbitrarily changed from 10 to 120 minutes and the film thickness obtained at that time was measured with a stylus type film thickness meter. went. The obtained results are shown in FIG.

[0019]

According to the present invention, a method for producing a thin film without patterning or restriction of a conductive substrate is established, and a thin film having higher performance can be obtained by a simple process. Therefore, the thin film produced by the method of the present invention can be used for laptop personal computers, word processors, workstations, aurora vision, liquid crystal projectors, liquid crystal televisions, overhead projectors (OHPs), instrument panels installed in vehicles,
Color filter of LCD panel for equipment monitor, equipment using electrophotographic photoreceptor (copying machine, laser printer), electronic device element applying aluminum as electrode (EL, sensor, solar cell, EC, LCD display, PDP display display It is widely and effectively used for an electrode), an element using a functional thin film (optical memory disk, PHB element, superconducting element, secondary nonlinear optical element, tertiary nonlinear optical element) and the like.

[Brief description of drawings]

FIG. 1 is a block diagram showing an example of the configuration of a cell for carrying out the method of the present invention.

FIG. 2 is a diagram showing an example of a light irradiation method.

FIG. 3 is a graph showing the change over time of the film thickness obtained in Example 2.

[Explanation of symbols]

 1: Photomask 2: Substrate 3: Spacer 4: Cell 5: Xenon lamp 6: Infrared absorption filter 7: Ultraviolet absorption filter 8: Band pass filter 9: Filter 10: Lens

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junichi Hanna 4259 Nagatsuta-cho, Midori-ku, Yokohama-shi, Kanagawa Tokyo Institute of Technology

Claims (2)

[Claims] 1. An inorganic substance or a hydrophobic organic substance is dispersed or solubilized in an aqueous medium using a surfactant composed of a ferrocene derivative, and a photooxidation catalyst in the range of 1 to 100 mM and a range of 1 to 100 mM are used. The pH of the micelle solution or dispersion obtained by adding the photo-oxidation catalyst regenerating substance in the range of 1: 5 to 5: 1 is adjusted to 5 or less, and then the substance to be formed is inserted into the micelle solution. Alternatively, the thin film of the inorganic substance or the hydrophobic organic substance is formed on the non-exposed portion of the film-forming substance by irradiating the contact surface between the dispersion liquid and the film-forming substance. Thin film manufacturing method. 2. The method for producing a thin film according to claim 1, wherein the photo-oxidation catalyst is a ruthenium complex and the photo-oxidation catalyst regenerator is a cobalt complex.