JP2001139890A - Electrodeposition liquid, cured electrodeposition film and its production method, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrodeposition liquid which can efficiently form an electrodeposition film in response to the change in pH of an aqueous solution in the vicinity of an electrodeposition substrate caused by the application of a relatively low potential to the substrate and which can give a durable cured electrodeposition film which, when once formed, hardly allows a polymer material to be eluted, a cured electrodeposition film and its production method, and an electronic device having a cured electrodeposition film. SOLUTION: An electrodeposition liquid is provided which contains an anionic polymer of which the solubility or dispersibility in an aqueous liquid rapidly changes with the change in pH and a curing agent for the anionic polymer. A cured electrodeposition film and its production method are provided together with an electronic device having a cured electrodeposition film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technology of a color filter used for various display devices such as a CCD camera and a liquid crystal display device and a color image sensor, and a printing technology of recording a fine pattern on various substrates.

[0002]

2. Description of the Related Art Currently, color filters are manufactured by (1) a dyeing method, (2) a pigment dispersion method, (3) a printing method,
(4) Ink jet method (5) Electrodeposition method and the like are known. In general, liquid crystal color filters use the photolithography method of the pigment dispersion method, which is one of the major factors in cost increase.However, considering the RGB filter layer and black matrix, high resolution, Controllability is also high. However, if the same level can be manufactured without using photolithography, the number of steps will be reduced, which can increase the yield and cost in the manufacture of color filters. . In addition, with the development of CPUs, color image documents have been enhanced in image quality and spread to society, and the demand for high-resolution reproduction technology and high reliability in the printing process has been increasing. Therefore, there is a strong demand for a simplified color filter manufacturing technique such as setting a color filter on a display driving board such as a TFT.

[0003] Among the above-mentioned color filter manufacturing methods,
In the electrodeposition method, a high voltage of about 100 V is applied to a pre-patterned transparent electrode in an electrolytic solution in which a pigment is dispersed in a water-soluble polymer, and an electrodeposition coating is performed by forming an electrodeposition film, This is repeated three times to obtain an RGB color filter layer. In this method, the electrodeposition potential is generally around 100 V, the foaming phenomenon due to the electrolysis of water is severe, the film surface property is poor,
In addition, since it is necessary to pattern the transparent electrode in advance by photolithography and create a power supply circuit for each pattern, the shape of the pattern is limited and it cannot be used for TFT liquid crystal. . Japanese Patent Application Laid-Open No. H11-105418 describes a low-potential electrodeposition method and an electrodeposition material for solving the drawbacks of such an electrodeposition method. However, when fabricating a plurality of filters for RGB using such materials, depending on the conditions, it is not possible to form a film efficiently with respect to a change in pH value, or a specific color film once electrodeposited (for example, When the substrate having R) is subsequently immersed in an electrodeposition solution for forming the next specific color film, the specific color film that has been deposited is eluted,
There is a problem that the water-soluble polymer component in the colored film is eluted when the protective layer is formed on the entire surface after the B filter is formed or during use of the device on which the filter is formed.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to apply a relatively low potential to an electrodeposited substrate to prevent a change in pH of an aqueous solution near the electrodeposited substrate. Electrodeposition liquid and electrodeposited film that can form an electrodeposited film efficiently and can form a robust electrodeposited cured film in which polymer materials are not easily eluted once formed. And an electronic device provided with an electrodeposition cured film.

[0005]

The above objects can be attained by providing the following electrodeposition liquid, electrodeposition cured film, a method for producing the same, and an electronic device. (1) An electrodeposition solution containing an anionic polymer whose solubility or dispersibility in an aqueous liquid changes rapidly due to a change in pH, and a curing agent for the anionic polymer. The electrodeposition liquid of the present invention, even when a voltage of a relatively low potential is applied to the electrodeposited substrate, an electrodeposited film is efficiently deposited in response to a pH change of an aqueous solution near the electrodeposited substrate, and Once formed, it is possible to form a robust electrodeposited cured film in which the polymer material is not easily eluted.

(2) The electrodeposition liquid according to (1), wherein the change in solubility or dispersibility occurs within a pH range of 2. (3) The electrodeposition liquid according to (1) or (2), wherein the curing agent is at least one thermosetting resin selected from the group consisting of a phenol resin, a urea resin, and a melamine resin. (4) The electrodeposition liquid according to (1) or (2), wherein the curing agent is at least one compound selected from a polyvalent epoxy compound and a polyvalent isocyanate compound.

(5) The above (1) or (2), wherein the curing agent is at least one metal compound selected from the group consisting of metal alkoxide compounds and polyvalent metal salts.
The electrodeposition liquid according to the above. (6) The above-mentioned (1) to (1), wherein the anionic polymer exhibits a cloud point (turbid point) in a pH range of 5.5 to 6.5 under the condition that the solid content concentration in water is 1% by weight or less. The electrodeposition liquid according to any one of 5).

(7) An electrodeposition solution for producing a color filter, wherein a colorant is further added to the electrodeposition solution according to any one of (1) to (6). (8) an anionic polymer whose solubility or dispersibility in an aqueous liquid rapidly changes due to a change in pH,
An electrodeposition liquid containing a curing agent of an anionic polymer and an adhesion improver.

(9) The electrodeposited substrate is brought into contact with the electrodeposited liquid according to any one of the above (1) to (8), and the pH value in the vicinity of the electrodeposited substrate is changed to thereby change the electrodeposited substrate. A method for producing an electrodeposited cured film, comprising depositing an electrodeposited film thereon and thereafter curing the electrodeposited film. (10) The electrodeposition substrate is brought into contact with an electrodeposition solution containing an anionic polymer whose solubility or dispersibility in an aqueous liquid changes rapidly due to a change in pH, and the pH value in the vicinity of the electrodeposition substrate is changed. Thus, a method for producing an electrodeposited cured film, comprising depositing an electrodeposited film on the electrodeposited substrate, then contacting the electrodeposited film with a curing agent, and then curing the electrodeposited film.

(11) An electrodeposition cured film produced by the method of (9). (12) An electrodeposition cured film produced by the production method of (10). The electrodeposition cured film of the present invention is a strong and durable electrodeposition cured film in which the polymer material is not easily eluted. (13) The above (11) or (1), wherein the electrodeposition cured film is adhered to the electrodeposited substrate via an adhesive material layer.
The electrodeposition cured film according to 2). (14) The electrodeposited cured film according to (13), wherein the adhesive material layer is made of an adhesive material having a functional group capable of chemically bonding to both the electrodeposited film and the electrodeposited substrate. (15) An electronic device comprising the electrodeposition cured film according to any one of (11) to (14) as an optical filter.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an electrodeposition solution containing an anionic polymer whose solubility or dispersibility in an aqueous liquid is rapidly changed by a change in pH, and an electrodeposition solution containing a curing agent for the anionic polymer. The film is deposited, and then the electrodeposited film is cured, or the electrodeposited film is deposited from the electrodeposited solution containing the anionic polymer, and then the solution containing the curing agent is brought into contact with the electrodeposited film, and then the electrodeposited film is deposited. It is characterized by being cured. "The solubility or dispersibility in an aqueous liquid is drastically changed by changing the pH" means that the substance in a dissolved or dispersed state in an aqueous liquid is precipitated by generating a supernatant by changing the pH. Means that. Such changes preferably occur within a pH range of 2, and more preferably within a pH range of 1.
By including an anionic polymer having this property in the electrodeposition liquid, it is possible to instantaneously deposit an electrodeposited film even with a steep pH change occurring near the electrode due to energization. Further, the cohesive force of the deposited film is high, and the re-dissolution rate in the electrodeposition liquid is reduced.

First, an anionic polymer whose solubility or dispersibility in an aqueous liquid rapidly changes when the pH changes will be described. Among ionic or other water-soluble polymers, there are substances whose solubility in water greatly changes due to changes in an oxidized state, a neutral state and a reduced state after forming an electrodeposited film. The change between these states can be performed by directly redoxing the polymer electrochemically or by changing the pH of the aqueous solution in which the polymer is dissolved. When these materials are dissolved in weakly alkaline water, the electrodes are immersed in the solution, and when a voltage is applied, H ions are generated on the electrodes on the anode side, thereby forming an electrodeposition film made of these polymer materials. You. For example, in a water-soluble acrylic resin, ions are dissociated and dissolved in water at a pH of 7 or more, but at a pH lower than that, a resin component is precipitated without ion dissociation. In general, the solubility of an anionic polymer having an anionic group (hydrophilic group) such as a carboxyl group greatly changes depending on the hydrogen ion concentration (pH) of a solution without a structural change. For example, some anionic polymers dissolve in water at pH 8 or higher, but precipitate at pH 5 or lower. Dissolve these materials in weakly alkaline water, disperse the pigment,
When the electrode is immersed in the solution and a voltage is applied, the pigment and the polymer are deposited on the electrode on the anode side to form an electrodeposition film in which the pigment and the polymer are mixed.

Specific examples of such an anionic polymer include a copolymer of an anionic monomer component and a hydrophobic monomer component. The anionic monomer may be any monomer that exhibits anionic properties in water, and is preferably a monomer having a polymerizable double bond and an anionic group (hydrophilic group) such as a carboxyl group, a hydroxyl group, or a sulfonic acid group inside. Wherein, for example, acrylic acid, methacrylic acid, hydroxyethyl methacrylate, acrylamide,
Maleic anhydride, fumaric acid, itaconic acid and derivatives thereof. In particular, the dissociated ion concentration pKa value is 3-5.
Is preferred. Such groups include carboxyl groups and the like. When the anionic group is a carboxyl group, the deposition efficiency of the image is particularly good and the robustness is high particularly in the electrodeposition phenomenon, and the hydrophilicity (high solubility in water) to the hydrophobicity (high solubility in water) due to pH change. (Low).

The hydrophobic monomer component includes an aromatic group such as an aryl group, a heterocyclic group such as pyridine, and a hydrophobic group such as a saturated or unsaturated hydrocarbon group such as an alkyl group or an alkoxy group. Examples include monomers having a polymerizable double bond, and specifically, alkyl acrylates such as styrene, α-methylstyrene, α-ethylstyrene, methyl acrylate, propyl acrylate, methyl methacrylate, and propyl methacrylate. In addition, lauryl methacrylate, acrylonitrile, vinyl acetate and the like and their derivatives are preferably used. Such a copolymer is
As a whole, the solubility parameter value SP value is 8.5 to 10.
Those in the range of 5 are preferred. The reason for this is that it has good affinity for the curing agent and the coloring material described later.

The number of hydrophobic groups relative to the sum of the number of hydrophobic groups and the number of hydrophilic groups in the monomer unit is 40 to 8
0% is preferable and 55-70% is more preferable. If the ratio of the number of hydrophobic groups is less than 40%, the water resistance and the film strength of the electrodeposited film may be insufficient, and if it exceeds 80%, the affinity of the ionic polymer for the aqueous solvent may be reduced. In some cases, the concentration of the electrodeposition liquid decreases, and the viscosity of the electrodeposition liquid becomes too high, so that a uniform electrodeposition film cannot be formed. On the other hand, when the number of the hydrophobic groups is in the above range, the affinity with the aqueous solvent is high, the liquidity of the electrodeposition liquid is stabilized, and the electrodeposition efficiency is high.

Among the above-mentioned anionic polymers,
In particular, at room temperature (15 ° C to 2
Anionic polymers exhibiting a cloud point (turbid point or polymer precipitation point) at a pH of 5.5 to 6.5 at 5 ° C) are most effective. The cloud point in the present invention is defined as a cloud point when the pH value of a transparent aqueous solution in which an anionic water-soluble polymer is dissolved is changed under normal temperature conditions (15 ° C. to 25 ° C.). Defined as the pH value at which clouding occurs. This is based on the phenomenon that, as the hydrogen ion concentration in the aqueous solution changes, the hydrogen ions (protons) and the anionic groups in the water-soluble polymer become hydrophobic and the water-soluble polymer becomes insoluble. In the measurement of the cloud point in the present invention, the pH of the aqueous solution is changed while the anionic (water-soluble) polymer is dissolved in water at room temperature so that the solid content concentration is 1% by weight or less. As a result, the haze generated in the aqueous solution is confirmed by optical means including visual observation. The above aqueous solution concentration is an aqueous solution concentration for confirming a cloud point, and does not limit the solid content concentration of an anionic polymer in an actual electrodeposition solution, but in an actual electrodeposition solution. The concentration of the anionic water-soluble polymer is generally 0
It is desirably set in the range of 0.10.01 to 50% by weight, preferably 0.1 to 20% by weight, and most preferably 0.5 to 10% by weight.

The electrodeposition mechanism will be described using a carboxyl group-containing water-soluble acrylic resin having an electrodeposition film forming ability as an example of the anionic polymer. This polymer easily dissolves in weakly alkaline water (pH 8 to 10) and exists as an anion in an aqueous solution. However, when the pH is 7 or less, the polymer is insolubilized and precipitates. When a platinum electrode is immersed in this aqueous solution and energized, OH − ions in the aqueous solution are consumed near the anode to become O ₂ , hydrogen ions increase, and the pH decreases.
This is because the following reaction occurs in which the hole (P) and the OH ^- ion are connected near the anode. 2OH- + 2p + ---> 1/2 (O2) + H2O In order for this reaction to take place, it is necessary to dissociate the water ions by applying a constant voltage. It increases and the pH drops. Therefore,
When a certain voltage or more is applied, H on the anode side of the electrode
The concentration of the ⁺ ions rises sharply, the solubility of the water-soluble carboxyl group-containing resin decreases and becomes insoluble, and a thin film of the insoluble water-soluble resin is formed on the positive electrode. In addition, the hydrophilicity of the hydrophilic group portion of the electrodeposited material is released by an energization phenomenon caused by application of a voltage, and an image pattern is instantaneously deposited.

[0018] The anionic polymer of the present invention comprises a p
It is preferable that the change in the H value from the solution state / dispersion state to the generation of supernatant from the dissolution state to the precipitation occurs within the pH range 2, and preferably within 1 in the pH range. By providing this characteristic, it becomes possible to instantaneously deposit a patterned electrodeposited film due to a sharp pH change due to energization. Further, the deposited electrodeposition film has a high cohesive force, and the re-dissolution rate in the electrodeposition solution is reduced.

Further, by adjusting the acid value of the anionic polymer in the present invention within the range of 60 to 200, good electrodeposition properties can be obtained. Particularly in the range of 70 to 140, better electrodeposition characteristics can be obtained. When the acid value of the anionic polymer is 60 or less, the solubility in the aqueous liquid becomes insufficient, so that the solid concentration of the electrodeposition liquid cannot be increased to an appropriate value, or the liquid becomes cloudy or precipitates are formed. This causes problems such as an increase in liquid viscosity. On the other hand, when the acid value of the anionic polymer is 200 or more, the formed film has high resolubility, low water resistance, and low electrodeposition efficiency with respect to the amount of electricity supplied.

The anionic polymer of the present invention is cured by using a curing agent described below after electrodeposition to increase the durability of the electrodeposited film. It is necessary to have a functional group such as an amino group, a carboxyl group, or a hydroxyl group.

Next, the curing agent used in the present invention will be described. Once the electrodeposited film is deposited from the electrodeposited solution containing the anionic polymer, the electrodeposited film once formed can be applied with a reverse voltage to the electrodes or at a higher pH value, e.g., pH10.
When the electrodeposited film is immersed in an aqueous solution of 1212, the electrodeposited film undergoes ion dissociation again and elutes again into the electrolytic solution, resulting in a decrease in the film. Therefore, after the electrodeposition, when water evaporates from the electrodeposition liquid or the like remaining on the electrodeposited film and the pH value of the electrodeposited film tends to elute, the film itself is easily dissolved, and the retention of the film is deteriorated. Will be done. When an RGB filter is formed by electrodeposition, after forming a monochromatic filter on the substrate, the substrate on which the monochromatic filter has been formed is immersed again in an electrodeposition solution in which a color pigment of another color is dispersed. Re-dissolution of the film may occur. Further, when the RGB filter comes into contact with moisture for some reason, the polymer component forming the electrodeposited film may be eluted. In the present invention, since the electrodeposited film is cured with the curing agent, such a re-elution phenomenon can be avoided. Specifically, a curing agent is added in advance to an electrodeposition solution containing water, an anionic polymer, and a coloring pigment, and the film can be cured at the same time as the formation of the electrodeposition film or after the formation of the electrodeposition film. After the electrodeposition film is formed on the substrate, the electrodeposition film can be cured by separately contacting the electrodeposition film with a solution in which a curing agent is dispersed or dissolved.

Specific examples of such a curing agent include the following. 1) Thermosetting resin Examples of the thermosetting resin include a phenol resin, a urea resin, and a melamine resin. Examples of the phenol resin include o-methylol phenol, p-methylol phenol, 2,4-dimethylol phenol, and 2,6. -Dimethylolphenol, 2,
Examples thereof include resols such as 4,6-trimethylolphenol and novolaks. Examples of the urea resin include methylol urea such as monomethylol urea, dimethylol urea, and trimethylol urea. Examples of the melamine resin include methylolmelamines such as monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, and hexamethylolmelamine.

2) Polyfunctional epoxy compound As the polyfunctional epoxy compound, a polyfunctional epoxy derivative such as a diglycidyl ether compound, a triglycidyl ether compound, a tetraglycidyl ether compound, or a haloepoxy compound can be used. In particular,
Glycidyl ether compounds of polyhydric alcohols such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glyceryl diglycidyl ether, glyceryl triglycidyl ether, bisphenol A
Examples include glycidyl ether compounds of aromatic polyhydric phenols such as diglycidyl ether, and haloepoxy compounds such as epichlorohydrin, epibromohydrin, and β-methylepichlorohydrin.

3) Polyfunctional Isocyanate Compound The polyfunctional isocyanate compound preferably has three or more isocyanate groups.
1,3,6-hexamethylene triisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-isocyanate-4
-Polyisocyanate monomers such as isocyanate methyl octane, triphenylmethane triisocyanate, and tris (isocyanate phenyl) thiophosphate are used. Among compounds containing three or more isocyanate groups, derivatives obtained from a polyisocyanate monomer are preferable in view of film-forming properties of a finally obtained crosslinked film, crack resistance, and ease of handling. It is more preferable to use a modified product such as a prepolymer or a prepolymer. Examples of these include urethane modified products obtained by modifying a polyol with an excess of the trifunctional isocyanate compound, buret modified products obtained by modifying a compound having a urea bond with an isocyanate compound, and allophanate modified products obtained by adding an isocyanate to a urethane group. Preferably, a modified isocyanurate, a modified carbodiimide, etc. are used.

Further, as a modified polyisocyanate, a blocked isocyanate reacted with a blocking agent for temporarily masking the activity of the isocyanate group can also be preferably used. The isocyanate used here may be two in addition to the one having three functional groups. Tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1,6- Hexamethylene diisocyanate, xylene diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate and the like are exemplified. Specifically, Sumidur N75, Sumidur N3200, Sumidur N3290 MPA / X, Sumidur N3290 EA, Sumidur N3400, Sumidur N3300, Sumidur N
3390 EA, Sumidur HT, Death Module Z4470 MPA
/ X, death module Z4470 EA death module Z4470 B
A, Death module E3265, Death module E4280, Sumidule L75, Sumidule L1375, Sumidule
L1365, Desmodur IL BA, SBU Isocyanate 0
817, Sumidur FL-2, Sumidur FL-3, Sumidur FL-4, Death Module HL BA, Death Module
E 1160, death module E1240, death module E136
1, Death module E14, Death module E 15, Sumidule E21-1 Sumidule E21-2, Death module E2
2, death module E23, death module E25, death module E2280, death module E27, death module
E29, Sumidur T-80, Sumidur 44S, Sumidur 44V10, Sumidur 44V20, Sumidur 44V
40, Sumidule 44V70, Death Module VL, Death Module VL-R10, Death Module VL-R20, Death Module VL-50, Death Module H, Death Module W, Death Module I (all of which are manufactured by Sumitomo Bayer) Isocyanate. Death Module CT Stable, Death Module BL 1100, Death Module BL1265 MPA / X, Sumidur BL3175, Death Module BL4265 SN, SBU
Isocyanate L805, Desmodur BL3370 MPA, Desmodur BL3475 BA / SN (all manufactured by Sumitomo Bayer)
And the like are used.

5) Metal alkoxide compound The following are examples of the metal alkoxide compound. Organic zirconium compounds such as zirconium chelate compounds, zirconium alkoxide compounds, zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents, aluminum chelate compounds, and organic aluminum compounds such as aluminum coupling agents In addition, antimony alkoxide compounds,
Germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelates, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, aluminum zirconium alkoxide compounds, and organic metal compounds such as aluminum zirconium alkoxide compounds In addition, tetramethoxysilane, tetraethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxy Examples include silane, methyltrimethoxysilane, dimethyldimethoxysilane, and the like. Among them, compounds having an alkoxysilyl group are particularly preferred.

6) Polyvalent metal salt By mixing one or more polyvalent metal salts as a curing agent into the electrodeposition solution, the electrodeposited film becomes a harder film, heat resistance is increased, and solvent resistance is improved. It is greatly improved, and the resolution and pattern shape of the produced pattern are greatly improved. Examples of the polyvalent metal salt include divalent or trivalent metal salts, and a calcium compound, a magnesium compound or a barium compound is particularly preferable in terms of hue and safety. For example, calcium salts include calcium carbonate, calcium phosphate, calcium peroxoborate, and the like, and magnesium salts include
Examples of magnesium carbonate, magnesium phosphate, magnesium orthosilicate, magnesium ammonium phosphate and the like, and examples of the barium salt include barium carbonate and barium phosphate.

When the curing agent is added to the electrodeposition solution in advance, the curing agent is mixed with the electrodeposition solution in the range of 0.005% by weight to 20.0% by weight in terms of solid concentration in the liquid, more preferably 0.05% by weight. It is mixed in the range of 4% by weight to 4% by weight. On the other hand, after the formation of the electrodeposited film, when the electrodeposited film is brought into contact with a solution containing a curing agent or is immersed in the solution to cure or crosslink the electrodeposited film, the same solid content concentration of the curing agent as described above is used. Solutions can be used. As for the method of adding a curing agent to the electrodeposition solution, if the curing agent is soluble or dispersible in the electrodeposition solution, it may be added directly to the electrodeposition solution. In this case, the curing agent may be dissolved in a water-soluble organic solvent, for example, a solvent such as isopropyl alcohol, and then added to the electrodeposition solution.

The curing treatment using the curing agent as described in the above 1) to 5) will be described by taking an RGB color filter as an example. For example, after the completion of the electrodeposition process of each of the RGB single color filters, further washing with water may be optionally performed. Thereafter, the electrodeposited film can be cured by heat-treating the electrodeposited film at a temperature in the range of 80 ° C. to 250 ° C. Alternatively, the curing process may be performed collectively after forming the RGB color filters without performing the curing process after each electrodeposition step. Further, the curing treatment in the present invention is not limited to the above-mentioned one, and can be carried out after completion of any electrodeposition step.

Next, the low potential electrodeposition method of the present invention using the above electrodeposition solution will be described in detail. In general, it has been shown that in order to produce an electrodeposited film, a threshold voltage at which an electrodeposition phenomenon occurs at a certain level or more is required, and if an electric current flows, the electrodeposited film is not necessarily formed. Therefore, when the electrodeposition potential does not exceed the threshold value, the electrodeposition phenomenon cannot be obtained. In the conventional electrodeposition technology, the voltage required for the electrodeposition material to form an electrodeposition film is as high as several tens mA / cm ² at about 50 V or more.
It cannot be applied to T. For example, in Dai Nippon Printing's patent “Method for manufacturing color filters and electrodeposited substrates for manufacturing color filters” (Japanese Patent Laid-Open No. 5-119209) and “Method for manufacturing color filters” (Japanese Patent Laid-Open No. 5-157905), the electrodeposition voltage is 20V
To 100V, and the electrodeposition material utilizes a redox reaction of a polymer. Thus, the electrodepositable polymer material generally well known as electrodeposition coating requires a voltage of 20 V or more for electrodeposition, and is practically mainly 100 V to 300 V in consideration of efficiency. . Therefore, for image formation,
Usually, external photoelectric effect characteristics such as ZnO ₂ for electrophotography were used, but they were not practical because they were water-based.

On the other hand, when an optical semiconductor is used, the photovoltaic power is 0.6 V even in crystalline Si with high efficiency, and photovoltaic power alone is not enough to form an image. Therefore, it is conceivable to raise the voltage by applying a bias voltage. However, if the voltage exceeds a certain voltage (a voltage depending on the band gap of the semiconductor to be used), the semiconductor and the solution necessary for forming the photovoltaic voltage are increased. The Schottky barrier between them breaks and an electrodeposition film is formed on the entire surface. Therefore, it is not possible to selectively form an image by the electrodeposition film only on the light-irradiated portion. There is a limit to the bias voltage that can be applied in this way, and therefore, image formation using photovoltaic power is limited to those that use photopolymerization of conductive polymers such as polypyrrole that redox at 1.0 V or less. .

However, in the present invention, since the anionic polymer whose solubility / dispersibility greatly changes in a very narrow range of pH as described above is used as the polymer material used in the electrodeposition solution, the polymer material has a voltage of 15 V or less. It is possible to form an electrodeposition film at a low voltage. In particular, it is possible to form an electrodeposition film by applying a voltage of 10 V or less, and even 5 V or less, which can be easily driven by a TFT, and to form an electrodeposition film using photovoltaic power. Therefore, for example, when forming a color filter layer using the low potential electrodeposition method of the present invention, a substrate provided with a TFT and a pixel electrode is immersed in an electrodeposition solution, and a low power drive of 5 V or less is used for the TFT. Thus, the color filter layer can be deposited on the pixel electrode as an electrodeposition film. In addition, a substrate in which an optical semiconductor thin film is formed on a light-transmitting electrode is used, and the substrate is immersed in an electrodeposition solution containing a color filter forming material, and a light is further applied while applying a bias voltage to the light-transmitting electrode. Is applied to generate a photoelectromotive force and apply a voltage necessary for electrodeposition, whereby a color filter layer can be deposited as an electrodeposition film on the light-irradiated portion. In either method, the pH near the substrate immersed in the electrodeposition solution is changed, and the difference in solubility of the polymer material due to the pH is used to deposit the electrodeposited film on the selected pixel electrode or on the light-irradiated part. The thin film can be selectively formed. By mixing one or more curing agents into the electrodeposition liquid used at this time, the electrodeposited film becomes a sufficiently hard film.

Next, the low potential electrodeposition method using the optical semiconductor will be described in detail below. Optical semiconductors (photovoltaic semiconductor materials) include Si, GaN, aC, BN, SiC,
ZnSe, TiO ₂ , GaAs-based compound, CuS, Zn3P2, phthalocyanine pigment-based material, perylene pigment-based material, azo pigment-based material, various organic photoconductive materials, etc. are used as a single layer or a plurality of layers. However, a high-purity substance or a single crystal system is required as the basic material, but it can also be used as a mixed substance. Further, a protective layer can be provided on the surface.

The thickness of the optical semiconductor layer is 0.05 μm to 3 μm.
The range of m is a use range in which good characteristics can be obtained. 0.
If it is less than 05 μm, the obtained photovoltaic power is too weak, which causes a problem in image formation. Further, when the thickness is in the range of 3 μm or more, charges generated by light are trapped in the layer, and the light hysteresis phenomenon becomes too large, causing a problem in image formation. In addition, in order to easily obtain the power required for film formation by the electrodeposition method, the configuration of the semiconductor layers is
It is composed of a single semiconductor, and mixing or inclusion of an insulating material such as a resin must be avoided. Mixing or inclusion of an insulating material such as a resin in the semiconductor layer also causes a large light hysteresis phenomenon. The semiconductor includes an n-type semiconductor and a p-type semiconductor, and any of the semiconductors can be used in the present invention. Further, if a stacked structure using a pn junction or a pin junction is used, more photocurrent flows and an electromotive force can be reliably obtained to improve the contrast, which is more desirable.

An example will be described using an n-type semiconductor as an example. When there is a Schottky barrier between the n-type semiconductor and the solution, the current flows in the forward direction when the semiconductor side is negative, but does not flow when the semiconductor side is positive. However, even when the semiconductor side is positive and no current flows, when the light is irradiated, an electron-hole pair is generated, the holes move to the solution side, and the current flows.
In this case, since the semiconductor electrode is made positive, the material to be electrodeposited must be negative ions. Therefore, a film is formed by a combination of an n-type semiconductor and an anionic molecular material, and a cationic molecular material is electrodeposited on a p-type semiconductor.

Next, TiO ₂ which is a particularly effective optical semiconductor among the above optical semiconductors will be described. TiO ₂ is a transparent oxide semiconductor in the visible region, and generates photovoltaic energy when irradiated with ultraviolet light. Therefore, a photo-deposited film can be formed on a transparent substrate by irradiating the substrate with ultraviolet light. Several methods are known for forming a TiO ₂ film. Reduction processing is performed to increase the conversion efficiency of photocurrent.
In the reduction treatment, it is usual to heat at about 550 ° C. in hydrogen gas. For example, Y. Hamasaki et al.
em. Soc. Vol. 141, No3.
Heat at 50 ° C for about 1 hour. But we have about 3
Sufficient effects were obtained with a low-temperature and short-time treatment at 60 degrees for 10 minutes. Thus, titanium oxide is transparent in the visible range,
Since it was possible to expose from the back and the light irradiation efficiency was good, it was shown to be very effective as a base material for producing a color filter. In recent years, titanium oxide having an excellent property as an n-type semiconductor has been economically obtained by various methods such as a sol-gel method, a sputtering method, and an electron beam evaporation method.

In general, the photovoltaic power of a semiconductor is only 0.6 V even with Si having a relatively large potential. However, materials that can be electrodeposited at 0.6V are limited. Therefore, it is necessary to compensate for the insufficient voltage by applying a bias voltage. The upper limit of the bias voltage that can be applied is up to the limit at which the Schottky barrier is maintained. When the Schottky barrier is broken, a current flows also in a region not exposed to light, and an electrodeposition film is formed on the entire region of the semiconductor substrate, so that an image cannot be formed. For example, if a material that is electrodeposited at 2.0 V is irradiated with light by applying a bias voltage of 1.5 V, the photovoltaic power of the semiconductor 0.6 V is added to 2.1 V, exceeding the threshold voltage required for electrodeposition, The photoelectric deposition film is formed only in the region irradiated with light.

Next, the conductivity and pH of the electrodeposition solution in the present invention
Is described. According to experiments, the conductivity can be translated into the electrodeposition speed, and the lower the resistivity in relation to the amount of electrodeposition, the thicker the electrodeposition film deposited over a certain period of time, but the volume resistivity is about 10Ω In cm, the rate of increase in the amount of electrodeposition tends to be saturated. The electric volume resistivity of the electrodeposition liquid is 1 to 10 ⁶ Ω
Electrodeposition is performed while controlling to a range of cm 2, and in this range, a good electrodeposition phenomenon can be performed. 10 ⁶ Ω · cm or more
In the range, a sufficient amount of current cannot be obtained, so that only a small amount of electrodeposition can be obtained. In the range of 1 Ω · cm or less, the controllability of the amount of electrodeposition deteriorates. Therefore, if the conductivity of the electrodeposition material ion alone is insufficient, the electrodeposition is affected. The electrodeposition speed can be controlled by adding Na ⁺ ions, NH 4 ⁺ ions, and Cl − ions PO 4 ³⁻ and SO 4 ²⁻ ions as ion examples. Further, the pH of the aqueous solution naturally affects the formation of the electrodeposited film. For example, if the electrodeposited film is formed under the condition that the solubility of the dye molecule is saturated before the electrodeposited film is formed, it is difficult to dissolve again after the film is formed. However, when the electrodeposited film is formed at the pH of the unsaturated solution, even if the electrodeposited film is formed, the film starts to be redissolved as soon as the energization is stopped.
Therefore, it is desirable to form the electrodeposited film at a pH of the solution at which the solubility is saturated.

Next, the removal of the unnecessary electrodeposition liquid on the electrodeposited substrate after the electrodeposition will be described. Immediately after the electrodeposition, an unnecessary electrodeposition liquid adheres to various places on the electrodeposited substrate. An effective means for removing the unnecessary electrodeposition liquid with high integrity is washing off by liquid washing. In particular, cleaning with an inert liquid that is transparent and highly safe is effective. However, since it is immediately after the electrodeposition, the newly formed electrodeposited film has insufficient strength both physically and chemically. Therefore, it is an effective method to wash the electrodeposited solidified film with a cleaning liquid, which promotes the solidification of the film as well as the unnecessary liquid. As a liquid having this effect, an aqueous liquid having a pH value at which the pH value is more likely to precipitate than the starting pH value of the electrodeposition liquid, that is, the electrodeposition film itself contacts the liquid to promote solidification and is unnecessary. The coloring material components of the electro-deposited liquid agglomerate and lose adhesion, and are easily washed off. The cleaning liquid using this phenomenon is a very effective means for this post-processing step. As a result, the pH value inside the electrodeposited film is also lower than that at the time of electrodeposition. The resolution is high and the resolution is high, resulting in highly accurate pattern formation. In order to further enhance the effect of the cleaning of the cleaning liquid and the hardening of the film, the pH value must be set at the starting point of the deposition of the electrodeposition liquid.
It is preferable that the pH value is set to a value that facilitates precipitation of 2 or more than the pH value.

The electrodeposition liquid of the present invention is particularly effective for forming a fine pattern such as a color filter. The electrodeposition solution for a color filter is prepared by dispersing a coloring material, i.e., a dye or a pigment, using an anionic polymer whose solubility or dispersibility in an aqueous liquid rapidly changes due to a change in the pH as described above. When the conductive polymer is deposited, a coloring material is simultaneously deposited to form a colored film.
Therefore, it is desirable that the anionic polymer is transparent. As the coloring material, it is preferable to use a pigment from the viewpoint of light resistance. Further, the hydrophobic group of the anionic polymer has a strong affinity for an organic pigment used as a coloring material, has an adsorption ability, and provides a good pigment dispersing function.

In the method for forming an electrodeposition film according to the present invention, a layer having good adhesion is provided on the electrodeposition substrate or on both the electrodeposition film and the substrate, and the electrodeposition film is formed thereon. It is effective. The adhesive layer material is not particularly limited as long as it has good adhesion to the conductive layer material of the electrodeposited substrate and has a functional group that can be bonded to the colored layer material to be deposited in the next step. That is, ITO that can be used as a conductive layer material
(Indium tin oxide film), tin oxide undoped with other elements, gold, platinum, aluminum, zinc,
Inorganic compounds such as carbon, metals or metal compounds, or conductive polymers such as polyacetylene, polypyrrole, polyaniline, polythiophene, and polyacene; electron-donating compounds (such as tetrathiafulvalene-based compounds) and electron-accepting compounds (tetracyanoquino Organic conductive materials such as charge transfer compounds such as quinodimethane compounds such as dimethane,
It is not particularly limited as long as it has good adhesiveness or can be bonded to a salt of C ₆₀ or C ₇₀ with an ion or the like, and has a functional group that can be bonded to a coloring layer material to be deposited in the next step.

Further, on the conductive material, titanium oxide, silicon oxide, germanium oxide, tin oxide, strontium titanate, barium titanate, magnesium titanate, calcium titanate, zinc oxide, tungsten oxide, strontium niobate, When an adhesive layer is formed after forming an elemental semiconductor such as zirconium oxide, tantalum oxide, zinc sulfide, silicon, and germanium, an oxide semiconductor, a compound semiconductor, and the like, the adhesiveness with the semiconductor is good or can be combined. It is only necessary to have a functional group that can be bonded to the colored layer material to be deposited.

However, in order to greatly improve the adhesiveness, a compound having a functional group capable of binding to the colored portion and having a functional group capable of binding to a conductive film or a semiconductor film material formed on the conductive film is particularly preferable. preferable. Conductive layer, semiconductor layer,
The type of bonding between the coloring layer and the adhesive layer is not particularly limited, and includes a covalent bond and an ionic bond. However, it is preferable to form a covalent bond from the strength of the bond. For example, by using γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, or the like, a covalent bond is formed between the conductive layer, the semiconductor layer, the coloring layer, and the adhesive layer. However, in order to maximize the covalent bond with the colored layer,
It is preferable that the functional group of the adhesive layer material that forms a bond with the coloring layer material has a small interaction with the conductive layer or the semiconductor layer material, and after forming a bond with the conductive layer or the semiconductor layer, It becomes possible to have a large amount on the side where the colored layer is formed. Although the material having such properties is not particularly limited, for example, the following general formula (1)
Compounds represented by (4) to (4) are preferred. Formula ^{(1) R 1 M 1 Y} 1 3 formula ^{(2) R 1 R 2 M} 1 Y 1 2 Equation ^{(3) R 1 R 2 R} 3 M 1 Y 1 Equation (4) R ¹ -SH

R ¹ represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group containing a functional group capable of binding to the coloring layer. The number of the functional groups in the R ¹ is not particularly limited, it is usually about 1 to 3. As the number of the functional groups increases,
By reacting with more colored layer materials, the colored layer materials can be more firmly fixed. R ² and R ³ represent the same group as R ¹ or a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group. . When R ² and R ³ are the same group as R ¹ , that is, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms including a functional group capable of binding to the coloring layer,
When it is an aromatic hydrocarbon group or a heterocyclic group, R ²
And R ³ may be the same or different from R ¹ . Further, R ² and R ³ may be the same or different. The M
¹ represents a tetravalent element other than carbon, and Y ¹ is
Represents a hydrolyzable functional group.

Specific examples of the functional group include a halogen group (halogen atom), an epoxy group and an ester group. Among these, halogen groups (halogen atoms),
An epoxy group is preferable, and a halogen group (halogen atom) is particularly preferable from the viewpoint of stability after the adhesive layer material is bonded to the conductive layer or the semiconductor layer. Specific examples of the ^{M 1, Si, Ge, Sn} , Ti, Zr and the like. Among these, Si and Ge are preferable, and Si is particularly preferable. The hydrolyzable functional group Y ¹ represents a halogen atom or an alkoxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Among these, chlorine, bromine and iodine are preferred. Examples of the alkoxy group include an alkoxy group such as a methoxy group, an ethoxy group, a normal or isopropoxy group, and an isocyano group.

Specific examples of the compounds represented by the above formulas (1) to (4) include p-bromophenyltrichlorosilane [pB
rPhSiCl ₃ ], p-bromophenyltrimethoxysilane [pB
rPhSi (OCH ₃ ) ₃ ], o-bromophenyltrichlorosilane [o-BrPhSiCl ₃ ], o-bromophenyltrimethoxysilane [o-BrPhSi (OCH ₃ ) ₃ ], m-bromophenyltrichlorosilane [m-BrPhSiCl ₃ ], M-bromophenyltrimethoxysilane [m-BrPhSi (OCH ₃ ) ₃ ], (p-bromomethyl)
Phenyltrichlorosilane [p-BrCH ₂ PhSiCl ₃ ], (p-bromomethyl) phenyltrimethoxysilane [p-BrCH ₂ PhS
i (OCH ₃ ) ₃ ], bromomethyltrichlorosilane [BrCH ₂
SiCl ₃ ], bromomethyltrichlorogermane [BrCH ₂ GeCl
₃ ], bromomethyltrimethoxysilane [BrCH ₂ Si (OCH
₃ ) ₃ ], bromomethyltrimethoxygermane [BrCH ₂ Ge
(OCH ₃ ) ₃ ], bromomethyltriethoxysilane [BrCH
₂ Si (OCH ₂ CH ₃ ) ₃ ],

Bromomethyldimethylchlorosilane [BrCH
_TwoSi (CH_Three)_TwoCl], bromomethyldimethylchlorogel
Man [BrCH_TwoGe (CH_Three)_TwoCl], 2-bromoethyl triclo
Losilane [CH_ThreeCHBrSiCl_Three], 2-bromoethyltrichloro
Germanic [CH_ThreeCHBrGeCl_Three], 1.2-dibromoethyltric
Lorosilane [BrCH_TwoCHBrSiCl_Three], 1.2-dibromoethylt
Lichlorogermane [BrCH_TwoCHBrGeCl_Three], 3-bromoprop
Rutrichlorogermane [Br (CH_Two)_ThreeGeCl_Three], 4-bromo
Butyldimethylchlorosilane [Br (CH_Two)_ThreeSi (CH_Three)
_TwoCl], 3-bromopropyltrichlorosilane [Br (CH_Two)
_ThreeSiCl_Three], 3-bromopropyltrimethoxysilane [Br
(CH_Two)_ThreeSi (OCH_Three)_Three], 3-bromopropyltriet
Xysilane [Br (CH_Two)_ThreeSi (OCH_TwoCH_Three)_Three], 8-Bro
Mooctyltrichlorosilane [Br (CH_Two)₈SiCl_Three], 8-
Bromooctyltrimethoxysilane [Br (CH_Two)₈Si (O
CH_Three)_Three], 8-bromooctyltriethoxysilane [Br
(CH_Two) ₈Si (OCH_TwoCH_Three)_Three],

8-bromooctyldimethylchlorosilane [B
r (CH ₂ ) ₈ Si (CH ₃ ) ₂ Cl], 11-bromoundecyltrichlorosilane [Br (CH ₂ ) ₁₁ SiCl ₃ ], 11-bromoundecyltrimethoxysilane [Br (CH ₂ ) ₁₁ Si ( OC
H ₃ ) ₃ ], 11-bromoundecyltriethoxysilane
[Br (CH ₂ ) ₁₁ Si (OCH ₂ CH ₃ ) ₃ ], 3-bromopropyltrichlorogermane [Br (CH ₂ ) ₃ GeCl ₃ ], bromomethyltribromogermane [BrCH ₂ GeBr ₃ ], p-chlorophenyltri Chlorosilane [p-ClPhSiCl ₃ ], p-chlorophenyltrimethoxysilane [p-ClPhSi (OCH ₃ ) ₃ ], m-chlorophenyltrichlorosilane [m-ClPhSiCl ₃ ], o-chlorophenyltrimethoxysilane [o-ClPhSi (OCH ₃₎ ) ₃ ], (p-
Chloromethyl) phenyltrichlorosilane [p-ClCH ₂ PhS
iCl ₃ ], (p-chloromethyl) phenyltrimethoxysilane [p-ClCH ₂ PhSi (OCH ₃ ) ₃ ], (p-chloromethyl) phenylmethyldichlorosilane [p-ClCH ₂ PhSi (CH ₃ ) Cl
₂ ], (p-chloromethyl) phenyldimethylchlorosilane [p-ClCH ₂ PhSi (CH ₃ ) ₂ Cl],

(P-chloromethyl) phenyltri-n-propoxysilane [p-ClCH ₂ PhSi (OnC ₃ H ₇ ) ₃ ], ((p-chloromethyl) phenylethyl) trichlorosilane [p-ClC
H ₂ Ph (CH ₂ ) ₂ SiCl ₃ ], ((p-chloromethyl) phenylethyl) methyldichlorosilane [p-ClCH ₂ Ph (CH ₂ )
₂ Si (CH ₃ ) Cl ₂ ], ((p-chloromethyl) phenylethyl) dimethylchlorosilane [p-ClCH ₂ Ph (CH ₂ ) ₂ Si
(CH ₃ ) ₂ Cl], ((p-chloromethyl) phenylethyl) trimethoxysilane [p-ClCH ₂ Ph (CH ₂ ) ₂ Si (OCH
₃ ) ₃ ], ((m-chloromethyl) phenylethyl) trichlorosilane [m-ClCH ₂ Ph (CH ₂ ) ₂ SiCl ₃ ], ((m-chloromethyl) phenylethyl) methyldichlorosilane [m
-ClCH ₂ Ph (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ ], ((m-chloromethyl) phenylethyl) dimethylchlorosilane [m-ClCH
₂ Ph (CH ₂ ) ₂ Si (CH ₃ ) ₂ Cl], ((m-chloromethyl) phenylethyl) trimethoxysilane [m-ClCH ₂ Ph
(CH ₂ ) ₂ Si (OCH ₃ ) ₃ ], ((o-chloromethyl) phenylethyl) trichlorosilane [o-ClCH ₂ Ph (CH ₂ ) ₂ S
iCl ₃ ],

((O-chloromethyl) phenylethyl) methyldichlorosilane [o-ClCH ₂ Ph (CH ₂ ) ₂ Si (CH ₃ ) C
l ₂ ], ((o-chloromethyl) phenylethyl) dimethylchlorosilane [o-ClCH ₂ Ph (CH ₂ ) ₂ Si (CH ₃ ) ₂ Cl],
((O-chloromethyl) phenylethyl) trimethoxysilane [o-ClCH ₂ Ph (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ], chloromethyltrichlorosilane [Cl ₃ CSiCl ₃ ], trichloromethyltrichlorosilane [ClCH ₂ SiCl ₃ ], trichloromethyltrichlorogermane [ClCH ₂ GeCl ₃ ], chloromethyltrimethoxysilane [ClCH ₂ Si (OCH ₃ ) ₃ ], chloromethyltriethoxysilane [ClCH ₂ Si (OCH ₂ CH ₃ ) ₃ , chloromethyl Trimethoxygermane [ClCH ₂ Ge (OCH ₃ ) ₃ ],
Chloromethyldimethylchlorosilane [ClCH ₂ Si (CH ₃ )
₂ Cl], chloromethylmethyldichlorosilane [ClCH ₂ Si
(CH ₃ ) Cl ₂ ], chloromethylmethyldiethoxysilane
[ClCH ₂ Si (CH ₃ ) (OCH ₂ CH ₃ ) ₂ ], chloromethylmethyldiisopropoxysilane [ClCH ₂ Si (CH ₃ ) (OCH
(CH ₃ ) ₂ ) ₂ ], bis (chloromethyl) dichlorosilane [(ClCH ₂ ) ₂ SiCl ₂ ],

Bis (chloromethyl) methylchlorosilane
[(ClCH_Two)_TwoSiCH_ThreeCl], 1-chloroethyltrichlorosi
Run [ClCHCH_ThreeSiCl_Three], 1,2-dichloroethyltrichloro
Silane [CH_TwoClCHClSiCl_Three], (Dichloromethyl) trik
Lorosilane [CHCl_TwoSiCl_Three], (Dichloromethyl) methyl
Dichlorosilane [CHCl_TwoSi (CH_Three) Cl_Two], (Dichlorome
Chill) dimethylchlorosilane [CHCl_TwoSi (CH_Three)_TwoCl],
2-chloroethyltrichlorosilane [Cl (CH_Two)_TwoSiC
l_Three], 2-chloroethyltriethoxysilane [Cl (CH_Two )_Two
Si (OCH_TwoCH_Three)_Three], 2-chloroethylmethyldichlorosi
Run [Cl (CH_Two)_TwoSiCl_TwoCH_Three], 2-chloroethylmethyl
Dimethoxysilane [Cl (CH_Two)_TwoSi (OCH_Three)_TwoCH_Three], 2-
(Chloromethyl) allyltrichlorosilane [CH_Two= C (CH_Two
Cl) SiCl_Three ], 1- (chloromethyl) allyltrichlorosila
[CH (CH_TwoCl) = CH_TwoSiCl_Three], 3-chloropropyltri
Chlorosilane [Cl (CH_Two)_ThreeSiCl_Three], 3-chloropropyl
Trichlorogermane [Cl (CH_Two)_ThreeGeCl_Three], 3-chlorop
Propyl dimethylchlorosilane [Cl (CH_Two)_ThreeSi (CH_Three)
_TwoCl],

3-chloropropyldimethylgermane [Cl (C
H_Two)_ThreeGe (CH_Three)_TwoCl], 3-chloropropylmethyldic
Lorosilane [Cl (CH_Two)_ThreeSi (CH_Three) Cl_Two], 3-chlorop
Ripylphenyldichlorosilane [Cl (CH_Two)_ThreeSiPhC
l_Two], 3-chloropropyldimethylmethoxysilane [Cl (C
H_Two)_ThreeSi (CH_Three)_Two(OCH_Three)], 3-chloropropyl
Limethoxysilane [Cl (CH_Two)_ThreeSi (OCH_Three)_Three], 3-k
Loropropyltriethoxysilane [Cl (CH_Two)_ThreeSi (OCH
_TwoCH_Three)_Three], 3-chloropropylmethyldimethoxysila
[Cl (CH_Two)_ThreeSiCH_Three(OCH_Three)_Two], 3-chloropropy
Methyldiethoxysilane [Cl (CH_Two)_ThreeSiCH_Three(OCH_Two
CH_Three)_Two], 4-chlorobutyldimethylchlorosilane [Cl
(CH_Two)_FourSiCl (CH_Three)_Two], 8-chlorooctyltrik
Lorosilane [Cl (CH_Two)₈SiCl_Three], 8-Chlorooctyl tilt
Limethoxysilane [Cl (CH_Two)₈Si (OCH_Three)_Three], 8-k
Lorooctyltriethoxysilane [Cl (CH_Two)₈Si (OCH
_TwoCH_Three) _Three], P-iodophenyltrichlorosilane [p-IP
hSiCl_Three)],

P-Iodophenyltrimethoxysilane [p-I
PhSi (OCH_Three)_Three], (P-iodomethyl) phenyltrik
Lorosilane [p-ICH_TwoPhSiCl_Three], (P-iodomethyl)
Phenyltrimethoxysilane [p-ICH_TwoPhSi (OCH_Three)_Three],
Iodomethyltrichlorosilane [ICH_TwoSiCl_Three], Iodine
Methyltrimethoxysilane [ICH_TwoSi (OCH_Three)_Three], Yaw
Demethyltriethoxysilane [ICH_TwoSi (OCH_TwoC
H_Three)_Three], 3-iodopropyltrichlorosilane [I (C
H_Two)_ThreeSiCl_Three], 3-Iodopropyltrimethoxysilane
[I (CH_Two)_ThreeSi (OCH_Three)_Three], 3-Iodopropyltrier
Toxisilane [I (CH_Two)_ThreeSi (OCH_TwoCH_Three )_Three], 8-Yaw
Dooctyltrichlorosilane [I (CH_Two)₈SiCl_Three], 8-
Iodooctyltrimethoxysilane [I (CH_Two)₈Si (OC
H_Three)_Three], 8-iodooctyltriethoxysilane [I (CH
_Two)₈Si (OCH_TwoCH_Three)_Three], (3-glycidoxypropyl
Le) trimethoxysilane [CH_TwoOCHCH_Two-O- (CH_Two)_ThreeSi
(OCH_Three)_Three], Acetoxyethyltrichlorosilane [CH
_ThreeCOOCH_TwoCH_TwoSiCl_Three], Acetoxyethyltriethoxy
Silane [CH_ThreeCOOCH_TwoCH_TwoSi (OCH_TwoCH_Three)_Three],

Acetoxyethyltrimethoxysilane [CH
₃ COOCH ₂ CH ₂ Si (OCH ₃ ) ₃ ], 3-bromopropylthiol [Br (CH ₂ ) ₃ SH], 8-bromooctylthiol [Br
(CH ₂ ) ₈ SH], 8-bromoundecylthiol [Br (C
H ₂ ) ₁₁ SH], p-bromophenylthiol [p-BrPhSH], o-
Bromophenylthiol [o-BrPhSH], m-bromophenylthiol [m-BrPhSH], (p-bromomethyl) phenylthiol [p-BrCH ₂ PhSH], 3-chloropropylthiol [Cl (C
H ₂ ) ₃ SH], 8-chlorooctylthiol [Cl (CH ₂ ) ₈ S
H], p-chlorophenylthiol [p-ClPhSH], o-chlorophenylthiol [o-ClPhSiH], m-chlorophenylthiol [m-ClPhSH], (p-chloromethyl) phenylthiol [p
-ClCH ₂ PhSH], 3-iodopropylthiol [I (CH ₂ ) ₃
SH], 8-iodooctylthiol [I (CH ₂ ) ₈ SH], p-iodophenylthiol [o-IPhSiH], m-iodophenylthiol [m-IPhSH], (p-iodomethyl) phenylthiol [p- ICH ₂ PhSH]. In these formulas, “Ph” represents a phenyl group.

Among the above-mentioned compounds, silane compounds are preferred because they are easy to synthesize, have a strong bond strength, and are abundant in variety. Among the compounds mentioned above, the formula (1) three Y ¹ in the case of those corresponding to the said formula (2) in the appropriate vital R ² is two in the case although the same as R ¹ Y ¹ And R ^2, and when the above (3) is satisfied and R ² and R ³ are the same as R ¹ , Y ¹ , R ^2, and R ³ are the same as those of the conductive layer or the semiconductor layer, respectively. Since it is bonded to a hydroxyl group or the like on the surface, there is an advantage that the bonding force with the conductive layer or the semiconductor layer per molecule of the adhesive layer material can be increased.

Further, among the above-mentioned compounds, a saturated or unsaturated aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 20 carbon atoms, wherein R ² corresponds to the above formula (2). When it is a group, Y ¹ and R ² are the same as the above (3), and R ² and R ³ are a saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group. In the case of a hydrogen group or a heterocyclic group, since only Y ¹ is bonded to a hydroxyl group or the like on the surface of the conductive layer or the semiconductor layer, respectively, the conductive layer or the semiconductor layer per molecule of the adhesive layer and Can be reduced, more adhesive layer material can be introduced to the surface of the conductive layer or semiconductor layer, and bonds can be formed with more colored layer materials. The adhesive layer material comprises:
The species may be used alone, or two or more species may be used in combination.

As a result of this reaction, the adhesive layer material is bonded to the surface of the conductive layer or the semiconductor layer, and a thin film of the adhesive layer material is formed on the conductive layer or the semiconductor layer. Since the bond is, for example, a chemical bond such as -M ¹ -O-, -S-, the conductive layer or the semiconductor layer and the adhesive layer material are strongly bonded, and a thin film of the adhesive layer material is used. Does not easily peel off from the conductive layer or the semiconductor layer. In addition,
At this time, in the adhesive layer material, the group bonded to the conductive layer or the semiconductor layer includes the halogen atom or the like,
A group other than a group selected from an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group;
In (4), R ¹ is not Y ¹ or —SH. Including the halogen atom, a group selected from an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group, the interaction with the conductive layer or the semiconductor layer is different from the other group in the adhesive layer material. Since it is relatively weak, it hardly reacts with the conductive layer or the semiconductor layer, but reacts with the coloring layer material thereafter.

The method for forming a layer made of the above-mentioned adhesive layer material on a conductive layer or a semiconductor layer (hereinafter sometimes referred to as a “base material”) is performed by dissolving at least one kind of the above-mentioned adhesive layer material in a solvent (hereinafter referred to as a solution). This may be referred to as “adhesive layer material solution”) and a substrate. Alternatively, the adhesive layer can be formed by vaporizing only the adhesive layer material or by bringing a vapor of the adhesive layer material and a mixed gas of a carrier gas (eg, nitrogen, argon, etc.) into contact with the substrate. As a result, a reaction occurs between the adhesive layer material and the conductive layer or the semiconductor layer, and the two are bonded. Heating can be performed as described below to promote the reaction. As the solvent, an organic solvent, for example, a hydrocarbon solvent,
Examples include ester solvents, ether solvents, halogen solvents, alcohol solvents, etc., water, and mixed solvents thereof. Examples of the hydrocarbon solvent include toluene, benzene, xylene, hexane, octane, hexadecane, cyclohexane and the like. Examples of the ester solvent include methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate and the like.
Examples of the ether solvent include dibutyl ether and dibenzyl ether. Examples of the halogen-based solvent include, for example, 1,1-dichloro-1-fluoroethane, 1,1-dichloro-2,2,2-trifluoroethane, 1,1
-Dichloro-2,2,3,3,3-pentafluoropropane, chloroform, dichloroethane, carbon tetrachloride and the like. Examples of the alcohol-based solution include methanol, ethanol, and i-propyl alcohol. In addition,
In the present invention, in addition to these, solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetic acid, and sulfuric acid may be used. As the water,
For example, tap water, distilled water, pure water and the like can be mentioned. Among these solvents, those used in the examples described below are preferable, and toluene, hexane, hexadecane, and the like have high processing efficiency and can form a clean thin film on the conductive layer or the semiconductor layer. preferable.

The concentration of the adhesive layer material in the solvent containing at least one of the adhesive layer materials is usually
1.0 to 100000 × 10 ^-4 mol / l, 1.0 to 100 × 10 ^-4 mo
l / l is preferred. When the concentration is less than 1.0 × 10 ⁻⁴ mol / l, it is not preferable because it takes a long time to immerse the substrate on which the conductive layer or the semiconductor layer is formed.
If it exceeds 10 ^-4 mol / l, the adhesive layer materials may react with each other, and a clean thin film may not be formed on the substrate.

The method of bringing the adhesive layer material solution into contact with the substrate includes, for example, immersing the adhesive layer material solution substrate, spraying the adhesive layer material solution onto the substrate by spraying or the like, It can be performed by applying a solution onto the base material by a casting method.

The time for bringing the adhesive layer material solution and the substrate into contact with each other is usually about several seconds to one week.
Minutes to one day are preferred. If the time is less than a few seconds, the treatment becomes insufficient, and the formula (1)
In some cases, the introduction of the compound represented by (4) is not sufficient, but even if it exceeds one week, there is no effect corresponding thereto, and the treatment efficiency is poor.

In order to promote this reaction and make the reaction proceed efficiently, it is effective to perform heating at about 30 to 120 ° C. or to apply ultrasonic waves during the contact. The heating may be performed after the contact. Also, before said contact,
It is also effective to wash the base material or perform a plasma treatment or a corona discharge treatment on the base material. The cleaning process is
For example, washing with an organic solvent such as methanol, ethanol and i-propyl alcohol, washing with an aqueous solution of an acid such as HF and HCl, washing with an aqueous solution of an alkali such as NH ₄ OH, UV /
Any of O ₃ cleaning, a combination thereof and the like may be used. Further, after contacting the adhesive layer material with the substrate and reacting both, to remove the unreacted adhesive layer material,
The substrate may be washed with an organic solvent such as n-hexadecane, decane, toluene, acetone, methanol and ethanol. As a method for forming the adhesive material layer on the substrate, a method in which the substrate is brought into contact with the adhesive layer material solution is preferable. A method of immersing the substrate is preferred.

In the present invention, in order to enhance the adhesiveness of the electrodeposited film to the electrodeposited substrate, in addition to the formation of the above-mentioned adhesive material layer, the adhesiveness of the electrodeposited film to the electrodeposited substrate is further added to the electrodeposition liquid. It is possible to employ a method of adding an enhancer.
As the adhesion enhancer therefor, it is possible to use the compounds represented by the formulas (1) to (4) used for forming the above-mentioned adhesive material layer.

Next, the black matrix will be described. The function of the black matrix layer is required to have both light shielding properties and light reflection preventing properties. Further, if the thickness of the black matrix layer is not small, it is difficult to form a fine pattern of the black matrix layer. That is, by forming a thin film that has both high light transmissivity and two functions of absorbing incident light instead of reflecting it,
Shows even better properties. In order to combine these functions, the metal thin film and the black pigment-dispersed resin-based thin film must have the high light-shielding ability of the metal thin film and the high light-absorbing property and the thinning possibility of the black pigment-dispersed resin-based thin film. And a black matrix layer having a composite layer structure. Further, the metal film is sometimes used as a wiring circuit conductive layer for power supply for TFT, and this wiring circuit conductive layer can be used as a black matrix. Next, a method for forming a black matrix will be described. The method of forming a black matrix using a conventionally known general photolithography, in the same manner as a color filter layer, or forming a black matrix only in a portion without a color filter layer using an ultraviolet curable resin There are methods. Various attempts have been made to achieve complete shielding, but this can be a major factor in increasing the cost of color filters.

In general, an electrodeposited film has a high insulating property,
It is necessary to perform a process of providing a transparent electrode layer for display by being laminated on the color filter layer. At this time, conduction between the transparent electrode (pixel electrode) for forming the filter portion and the display transparent electrode layer provided on the filter layer is also taken at the end where the layers are laminated.

[0066]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. Example 1 A thin film transistor (TFT) is formed on a 0.9 mm-thick non-alkali glass substrate by a conventional method, and then a light-transmissive ITO pixel electrode for forming a color filter layer of each color is formed by a photolithography method. To form an electrodeposited substrate. The gate and drain electrodes of the TFT were formed of laminated aluminum electrodes. Next, a copolymer of styrene-acrylic acid-acrylate (number average molecular weight 1
6,000 hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 70%,
A phenol resin (manufactured by Shoei Chemical Industry Co., Ltd., trade name) in an aqueous dispersion containing an acid value of 120, a cloud point of pH 6.1) and an anthraquinone-based red fine particle pigment in an amount of 5.0% by weight, respectively.
(Resin) was dissolved at 5% by weight, and the pH was adjusted with an aqueous phosphoric acid solution and an aqueous ammonia solution to obtain an electrodeposition solution (pH 7.9, volume resistivity 2 × 10 ² Ω · cm). The electrodeposited substrate is immersed in an electrodeposition solution using an electrodeposition apparatus having a triode arrangement generally used in the electrochemical field, and a selected TFT corresponding to a red pixel of a final color filter is turned on.
In this state, a voltage was applied for 3 seconds to 2.7 V with respect to the saturated calomel electrode using the selected pixel electrode as a working electrode. A red colored film was formed on the selected pixel electrode. Then, using washing water having a pH value of 6.5,
Unnecessary adherent electrodeposition liquid was washed away, and heat-treated at 150 ° C. for 1 hour to complete a red filter portion.

A similar electrodeposition solution (pH 7.9, volume resistivity 2 × 10 ² Ω · cm) was prepared and pigmented under the same conditions, except that a phthalocyanine green ultrafine particle pigment was used as the pigment. A film was formed on each pixel electrode. Then, a pH value of 6.5
Unnecessary electrodeposition liquid is washed away using the washing water of
Heat treatment was performed at 0 ° C. for 1 hour to complete a green filter portion. Similarly, the same electrodeposition solution (pH 7.9, volume resistivity value) except that a phthalocyanine blue ultrafine particle pigment was used as the pigment.
2 × 10 ² Ω · cm) and deposited under the same conditions to form a blue colored film on each pixel electrode. Next, unnecessary washing of the electrodeposition solution was washed away using washing water having a pH value of 6.5, and the solution was washed at 150 ° C.
For 1 hour to complete a blue filter portion.

Next, the electrodeposited substrate on which the filter portion was formed as described above was subjected to a heat treatment at 230 ° C. for 30 minutes to further harden the film. Thereafter, ITO was deposited on this surface by a sputtering film forming method, and then removed by photolithography except for a portion corresponding to a color filter, thereby forming a transparent display electrode portion on an upper layer portion of the filter portion. Next, a conductive path between the display electrode portion and the ITO film as a lower pixel electrode was secured. Through the above steps, a color filter integrated with a TFT drive circuit was completed.

This color filter has a pencil hardness of 3H.
In a solvent such as acetone, IPA, N-methylpyrrolidone
The film did not change even after immersion for 0 minutes, and the durability was good.

Example 2 An electrodeposited substrate was produced in the same manner as in Example 1 except that the thickness of the glass substrate was 0.7 mm. Next, a styrene-acrylic acid random copolymer (molecular weight 14,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 73%, acid value 90, glass transition point 45)
℃, flow start point 90 ℃, decomposition point 247 ℃, cloud point pH 5.8),
The azo red ultrafine particle pigment was added to an aqueous dispersion having a solid content of 8% by weight and dispersed at a solid content ratio of 5: 5, and dimethylaminoethanol was further added to a concentration of 210 mmol / liter. 5% by weight of a methylol urea resin (manufactured by Oshika Shinko Co., Ltd., trade name: Oshika Resin) is added to this pigment dispersion.
Mix and stir to dissolve the electrodeposition solution (pH 7.9,
A volume resistance value of 5 × 10 ² Ω · cm) was obtained.

The electrodeposited substrate is immersed in an electrodeposition solution using an electrodeposition apparatus having a three-electrode arrangement generally used in the electrochemical field,
The selected TFT corresponding to the red pixel of the final color filter is turned on, and the selected pixel electrode is used as a working electrode, and 2.5 V is applied to the saturated calomel electrode.
A voltage was applied for 4.5 seconds so that A red colored film was formed on the selected pixel electrode.

The same electrodeposition solution (pH) was used except that a phthalocyanine green-based ultrafine particle pigment was used as the pigment, and the concentration of dimethylaminoethanol was 200 mmol / liter.
7.9, volume resistivity 5 × 10 ² Ω · cm). Electrodeposition was performed under the same conditions except that a voltage of 2.8 V was applied for 3 seconds to form a green colored film on the selected pixel electrode. Thereafter, cascade cleaning was sufficiently performed with a pH adjusting liquid having a pH value of 4.2.

Similarly, the same electrodeposition solution (pH 7.9, volume resistance value 5 × 10 ²⁾ was used except that a phthalocyanine blue-based ultrafine particle pigment was used as the pigment and the concentration of dimethylaminoethanol was 190 mmol / liter. Ω · cm). Electrodeposition was performed under the same conditions except that a voltage of 2.5 V was applied for 5 seconds to form a blue colored film on the selected pixel electrode.

Next, carbon black black pigment particles (having a carboxyl group on the surface) having an average particle diameter of 13 nm were added in an amount of 5% by weight based on the total weight of the liquid, and a photosensitive polymer material (manufactured by Toa Gosei Chemical Co., Ltd .; (Name: Arontite) The whole of the electrodeposited substrate with the colored film was immersed in a dispersion solution in which 0.8% by weight and the balance of pure water were ultrasonically dispersed. Thereafter, pattern exposure was performed, and a black film was deposited on conductive portions other than the portion corresponding to the colored filter film. A black matrix / protective layer of a 0.6 μm thick insulating carbon black particle thin film was formed. The optical transmission density of this black matrix film was 2.2.

Next, the electrodeposited substrate on which the filter layer was formed as described above was placed in a heating oven at 220 ° C. and allowed to stand for 1 hour to harden the electrodeposited film and remove the pH adjuster.
Thereafter, ITO was deposited on this surface by a sputtering film forming method, and then removed by photolithography except for a portion corresponding to the color filter, and a transparent display electrode portion was formed on the upper layer portion of the color filter portion. . Next, this display electrode portion and ITO, which is a lower pixel electrode, are used.
A conductive path with the film was secured. Through the above steps, a color filter integrated with a TFT drive circuit was completed. When the optical characteristics of the boundary between the filter portion and the black matrix portion were evaluated, the deviation of the boundary edge portion was within 3.6 μm, and it was confirmed that a highly accurate color filter was obtained.

Example 3 A transparent conductive layer of ITO was formed to a thickness of 0.1 μm on a quartz glass substrate having a thickness of 0.7 mm by sputtering, and TiO ₂ of 0.2 μm was formed by a sol-gel method, followed by heat treatment at 500 ° C. Done. Next, in order to improve the photocurrent characteristics of TiO _2, a reduction treatment was performed by annealing at 460 ° C. for 10 minutes in pure nitrogen gas mixed with 4% hydrogen gas, thereby producing an electrodeposited substrate. Next, a styrene-acrylic acid random copolymer (molecular weight
13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 73%, acid value 9
0, glass transition point 75 ° C, flow start point 110 ° C, decomposition point 247
C., cloud point pH 5.8) and an aqueous dispersion of an azo red ultrafine particle pigment having a solid content ratio of 5: 5 at a solid content of 6% by weight, and a melamine resin (Oshika Shinko Co., Ltd.) (Trade name: Oshika Resin), a 10% by weight isopropyl alcohol solution was mixed and dispersed while stirring so as to be 5% by weight with respect to the above aqueous dispersion, and an electrodeposition solution (pH 8.1, volume resistance value)
2 × 10 ² Ω · cm).

Using an electrodeposition apparatus having a tripolar arrangement commonly used in the electrochemical field, the above electrodeposited substrate is immersed in an electrodeposition liquid,
Then, a TiO ₂ electrode was used as a work electrode for the saturated calomel electrode, and a 1.7 V bias potential was applied to the work electrode. Mercury xenon lamp (Yamashita Denso,
When the light was irradiated for 3 seconds using a photomask of a mask pattern image with a light intensity of 365 nm at a light intensity of 50 mW / cm ² ), a red colored film was formed only on the TiO ₂ surface where the transmitted light was irradiated. .

Next, a phthalocyanine green-based ultrafine pigment was used as the pigment, and the melamine resin was used instead of the melamine resin.
2-phenyl-4,6-bis (trichloromethyl) -s
-An electrodeposition solution for a green filter (pH 8.1, volume resistivity value) in the same manner as the electrodeposition solution for a red filter except that a 1% by weight isopropyl alcohol solution of triazine is added to 5% by weight based on the aqueous dispersion. 2 × 10 ² Ω · cm). Electrodeposition was performed under the same conditions as above except that the light irradiation time was changed to 4 seconds. A green mask filter pattern was formed only in the region where light was irradiated on the TiO ₂ surface. Then pH
The cascade cleaning was sufficiently performed with a pH adjusted liquid having a value of 4.5.

Next, an electrodeposition solution for a blue filter (pH 8.1, volume resistivity 2 × 10 ² Ω · cm) was prepared in the same manner as the electrodeposition solution for a red filter except that a phthalocyanine blue-based ultrafine particle pigment was used as a pigment. ) Was prepared. 1.8V working electrode
The electrodeposition was performed under the same conditions as in the case of electrodeposition of the red filter except for the above. A blue colored film was formed only in the area where the transmitted light was irradiated on the TiO ₂ surface.

Next, carbon black (pH value 3.5, average particle diameter 34 nm, oil absorption (DPB) 70
cc / 100 g) (except that the solid content ratio with the electrodepositable polymer is 2 to 8), except that the electrodeposition solution for black matrix (pH 8.1, volume resistivity 2 × 10 ² Ω · cm) was prepared.
Electrodeposition was performed under the same conditions as for the red filter electrodeposition. A black matrix pattern having a black thickness of 0.7 μm was formed only in the region where light was irradiated on the TiO ₂ surface. The optical transmission density of the black matrix film was 2.5.

Next, the electrodeposited substrate on which the filter layer was formed as described above was placed in an oven at 210 ° C. and heated for 1 hour to perform a hardening treatment of the electrodeposited film. On top of this, a protective layer was coated to form a color filter. When the optical characteristics of the boundary between the filter portion and the black matrix portion of the produced color filter were evaluated, a high accuracy of deviation of the boundary edge portion within 5 μm was achieved. When an ultrasonic durability test (10 hours) was performed using an organic solvent, the initial sample form could be maintained. On the other hand, in the sample to which the curing agent was not added, cracks and detachment occurred partially in the film.

Example 4 An ITO transparent conductive film having a thickness of 0.1 μm was formed on a non-alkali glass substrate having a thickness of 0.5 mm by a sputtering method.
TiO ₂ was formed to a thickness of m by the sol-gel method and heated at 500 ° C. for 30 minutes. Next, in order to improve the photocurrent characteristics of TiO ₂ , annealing was performed at 360 ° C. for 20 minutes in pure nitrogen gas mixed with 5% hydrogen gas as a reduction treatment to obtain an electrodeposited substrate. Styrene-acrylic acid random copolymer (molecular weight
22,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 70%, acid value 1
00, glass transition point 55 ° C, flow start point 94 ° C, decomposition point 254
C, cloud point pH 5.9) and ultra-fine pigment of carbon black (pH value 2.5, average particle size 21 nm, oil absorption (DPB) 110cc / 100g) in a solid content ratio of 3 to 7 An aqueous dispersion having a concentration of 6% by weight was prepared, and a 10% by weight solution of a phenol resin in dioxane was mixed with the aqueous dispersion while stirring so as to be 5% by weight, and an electrodeposition solution for black matrix (pH 7.8) was prepared. , Volume resistivity 1 × 10 ² Ω · cm). Using an electrodeposition apparatus having a triode arrangement commonly used in the electrochemical field, immersing the electrodeposited substrate in an electrodeposition solution, and using a TiO ₂ electrode as a work electrode with respect to a saturated calomel electrode, At a bias potential of 1.7V.
Mercury xenon lamp (Yamashita Denso, wavelength
When the light was irradiated for 2 seconds using a photomask of a mask pattern image with a light intensity of 365 nm and a light intensity of 50 mW / cm ² ),
A black pattern having a thickness of 1.2 μm was formed only in the area where the transmitted light was irradiated on the TiO ₂ surface. Then pH 4.5
The cascade cleaning was sufficiently performed with the H adjustment liquid. As a result, a black matrix layer having a uniform layer thickness was formed. The optical transmission density of this black matrix film is 2.6
Met.

Next, a styrene-acrylic acid copolymer (molecular weight 14,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 73%,
Acid value 89, glass transition point 42 ° C, flow start point 97 ° C, decomposition point 23
8 ° C, cloud point pH 6.3) and an aqueous dispersion of 6% by weight of solid content in which an azo red ultrafine particle pigment is dispersed at a solid content ratio of 6: 4, and a phenol resin as a curing agent A 10% by weight dioxane solution was mixed with stirring to 5% by weight with respect to the aqueous dispersion to prepare an electrodeposition solution (pH 7.8, volume resistivity 1 × 10 ² Ω · cm). 1.8 for work electrode
Electrodeposition was performed under the same conditions as for the black matrix electrodeposition except that a voltage of V was applied and the light irradiation time was set to 6 seconds.
A red mask filter pattern was formed only in the region where the light was irradiated on the TiO ₂ surface. Thereafter, the substrate was washed with a pH adjusting liquid having a pH value of 4.8.

Next, in place of the azo red ultrafine particle pigment,
An electrodeposition solution for a green filter (pH 7.8, volume resistivity 1 × 10 ² Ω · cm) was prepared under the same conditions as the electrodeposition solution for a red filter except that a phthalocyanine green-based ultrafine particle pigment was used. Electrodeposition was performed under the same conditions as for the red filter electrodeposition except that the light irradiation time was 7 seconds. A green mask filter pattern was formed only in the region where light was irradiated on the TiO ₂ surface. Thereafter, the plate was washed with a pH adjusting liquid having a pH value of 4.7.

Next, in place of the azo red ultrafine particle pigment,
An electrodeposition solution for a blue filter (pH 7.8, volume resistivity 1 × 10 ² Ω · cm) was prepared under the same conditions as the electrodeposition solution for a red filter except that a phthalocyanine blue-based ultrafine particle pigment was used. Electrodeposition was performed under the same conditions as for the red filter electrodeposition except that a voltage of 1.9 V was applied to the work electrode and the light irradiation time was set to 7 seconds. A blue mask filter pattern was formed only in the region where light was irradiated on the TiO ₂ surface. Next, the pH value
It was washed with a pH adjusted liquid of 4.2.

The electrodeposited substrate on which the color filter pattern was formed was placed in a heating oven at 190 ° C. and heat-treated for 60 minutes to complete the hardening treatment of the electrodeposited film. 2 on this membrane
A pencil scratch test of H demonstrated that the film was a hard film that did not scratch. A protective layer was coated thereon to complete the color filter.

Example 5 An electrodeposited substrate was produced in the same manner as in Example 1. Next, a copolymer of styrene-acrylic acid-acrylic acid ester (number-average molecular weight: 16,000 hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 70%, acid value 120, cloud point pH 6) and anthraquinone red An aqueous dispersion containing 5.0% by weight of each of fine particle pigments as a solid content concentration was prepared, and 0.5% by weight of tetramethoxysilane was dissolved therein as a curing agent.
, 2 × 10 ² Ω · cm). Using an electrodeposition apparatus having a three-pole arrangement common in the electrochemical field,
The electrodeposited substrate is immersed in an electrodeposition liquid so that the selected TFT corresponding to the red pixel of the final color filter is turned on, and the selected pixel electrode is used as a working electrode, and a saturated calomel electrode is used. The voltage was applied for 3 seconds so that the voltage became 2.7 V. A red colored film was formed on the selected pixel electrode. Next, unnecessary adhesion electrodeposition liquid was washed away using washing water having a pH value of 6.5 to complete a red filter portion.

An electrodeposition solution similar to the above-mentioned electrodeposition solution for a red filter was prepared, except that an ultrafine particle pigment of phthalocyanine green was used as a pigment, and a green colored film was formed under the same conditions. Next, unnecessary adhesion electrodeposition liquid was washed away using washing water having a pH value of 6.5 to complete a green filter portion.

An electrodeposition solution similar to the above-mentioned electrodeposition solution for a red filter was prepared, except that an ultrafine particle pigment of phthalocyanine blue was used as a pigment, and a blue colored film was formed under the same conditions. Next, unnecessary adhesion electrodeposition liquid was washed away using washing water having a pH value of 6.5 to complete a blue filter portion.

Next, the electrodeposited substrate on which the filter portion was formed was subjected to a heat treatment at 230 ° C. for 30 minutes to further harden the film. After that, ITO is deposited on this surface by a sputtering film forming method, and then, by a photolithographic method,
Only the portion corresponding to the color filter was removed and removed, and a transparent display electrode portion was formed in the upper layer portion of the color filter portion. Next, a conductive path between the display electrode portion and the ITO film as a lower pixel electrode was secured. Through the above steps, a color filter integrated with a TFT drive circuit was completed.

This color filter has a pencil hardness of 3H.
In a solvent such as acetone, IPA, N-methylpyrrolidone
There was no change in the film even after immersion for 0 minutes, and the film was durable.

Example 6 An electrodeposited substrate was produced in the same manner as in Example 1. Styrene-acrylic acid-acrylic acid ester copolymer (number-average molecular weight 16,000 hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 70)
%, Acid value 120, cloud point pH 6) and an electrodeposition dispersion (pH 7.9, volume resistivity 2 × 10 ² Ω · cm) containing 5.0% by weight of anthraquinone-based red fine particle pigment as a solid content respectively. did. The electrodeposited substrate is immersed in an electrodeposition solution using an electrodeposition apparatus having a triode arrangement commonly used in the electrochemical field, and the selected TFT corresponding to the red pixel of the final color filter is turned on. , And a voltage was applied for 3 seconds so that the voltage became 2.7 V with respect to the saturated calomel electrode using the selected pixel electrode as a working electrode. A red colored film was formed on the selected pixel electrode. Next, unnecessary adhesion electrodeposition liquid was washed away using washing water having a pH value of 6.5 to complete a red filter portion.

After drying the electrodeposited substrate on which the red filter portion was formed, tolylene diisocyanate (TDI) was added at 2% by weight.
After dipping in the dissolved toluene solution and contacting for 5 seconds, unnecessary adhesion liquid was washed and removed, and heat-cured at 100 ° C. for 10 minutes.

An electrodeposition solution similar to the above-mentioned electrodeposition solution for a red filter was prepared, except that an ultrafine particle pigment of phthalocyanine green was used as a pigment, and a green colored film was formed under the same conditions. Next, unnecessary adhesion electrodeposition liquid was washed away using washing water having a pH value of 6.5 to complete a green filter portion.

An electrodeposition solution similar to the above-mentioned electrodeposition solution for a red filter was prepared, except that an ultrafine particle pigment of phthalocyanine blue was used as a pigment, and a blue colored film was formed under the same conditions. Next, unnecessary adhesion electrodeposition liquid was washed away using washing water having a pH value of 6.5 to complete a blue filter portion.

Next, the electrodeposited substrate on which the filter portion was formed was subjected to a heat treatment at 230 ° C. for 30 minutes to further harden the film. After that, ITO is deposited on this surface by a sputtering film forming method, and then, by a photolithographic method,
Only the portion corresponding to the color filter was removed and removed, and a transparent display electrode portion was formed in the upper layer portion of the color filter portion. Next, a conductive path between the display electrode portion and the ITO film as a lower pixel electrode was secured. Through the above steps, a color filter integrated with a TFT drive circuit was completed.

This color filter has a pencil hardness of 3H.
In a solvent such as acetone, IPA, N-methylpyrrolidone
There was no change in the film even after immersion for 0 minutes, and the film was durable.

Example 7 An electrodeposited substrate was produced in the same manner as in Example 1 except that the thickness of the glass substrate was 0.7 mm. Styrene-acrylic acid random copolymer (molecular weight 14,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 73%, acid value 90, glass transition point 45 ° C, flow starting point 90 ° C, decomposition point 247 ° C, cloudy PH 5.8) and an aqueous dispersion of azo-based ultrafine particle pigment dispersed at a solid content ratio of 5: 5 at a solid content of 6% by weight, and a concentration of dimethylaminoethanol of 210 mmol / liter. Was mixed as follows. Next, tetraethylene glycol diglycidyl ether as a curing agent was mixed and stirred into this solution so as to be 5% by weight with respect to the copolymer, and an electrodeposition solution (pH 7.9, volume resistance value 2 × 10 ² Ω · cm) was added. ) Got. The electrodeposited substrate is immersed in an electrodeposition solution using an electrodeposition apparatus having a triode arrangement commonly used in the electrochemical field, and the selected TFT corresponding to the red pixel of the final color filter is turned on. , And a voltage was applied for 4.5 seconds to 2.5 V with respect to the saturated calomel electrode using the selected pixel electrode as a working electrode. A red colored film was formed on the selected pixel electrode. Thereafter, cascade cleaning was sufficiently performed with a pH adjusted liquid having a pH value of 4.2.

Next, the same procedure as in the electrodeposition solution for red filter was carried out except that the azo red ultrafine particle pigment was replaced with a phthalocyanine green ultrafine particle pigment, and that the amount of dimethylaminoethanol was 200 mmol / liter. Electrodeposition solution for green filter (pH 7.9, volume resistivity 2 × 10 ² Ω ・
cm). The above voltage was applied at 2.8 V for 3 seconds. A green colored film was formed on the selected pixel electrode. Thereafter, cascade cleaning was sufficiently performed with a pH adjusted liquid having a pH value of 4.2.

Next, the same procedure as in the electrodeposition solution for red filter was carried out except that the azo red ultrafine particle pigment was replaced with a phthalocyanine blue ultrafine particle pigment and that the amount of dimethylaminoethanol was 190 mmol / liter. Electrodeposition solution for blue filter (pH 7.9, volume resistivity 2 × 10 ² Ω · c
m) was prepared. The above voltage was applied at 2.5 V for 5 seconds. A blue colored film was formed on the selected pixel electrode. Thereafter, cascade cleaning was sufficiently performed with a pH adjusted liquid having a pH value of 4.2.

The electrodeposited substrate on which the three colored portions were formed was heated at 100 ° C.
-Heating was performed for 24 hours to perform crosslinking. The colored portion after cross-linking was durable with no change in the film even after a scratch resistance test with a pencil hardness of 3H or immersion in a solvent such as acetone, IPA, N-methylpyrrolidone for 10 minutes.

Next, carbon black black pigment particles (having a carboxyl group on the surface) having an average particle diameter of 13 nm were added in an amount of 5% by weight based on the total weight of the liquid and a photosensitive polymer material (trade name, manufactured by Nogawa Chemical Co., Ltd. : Diabond) The entirety of the electrodeposited substrate having the colored film formed thereon was immersed in a dispersion solution in which 0.8% by weight and the balance of pure water were ultrasonically dispersed. Thereafter, pattern exposure was performed, and a black film was deposited on conductive portions other than the portion corresponding to the colored filter film. A black matrix / protective layer of a 0.6 μm thick insulating carbon black particle thin film was formed. The optical transmission density of this black matrix film was 2.2.

Next, the electrodeposited substrate on which the filter portion was formed was placed in a heating oven at 220 ° C. and left for 1 hour to further harden the electrodeposited film and to remove the pH adjusting agent. Thereafter, ITO was deposited on this surface by a sputtering film forming method, and then removed by photolithography except for a portion corresponding to the color filter, and a transparent display electrode portion was formed on the upper layer portion of the color filter portion. .
Next, the display electrode section and the lower pixel electrode IT
A conductive path with the O film was secured. Through the above steps, a color filter integrated with a TFT drive circuit was completed.

Example 8 An electrodeposited substrate was produced in the same manner as in Example 1. Next, a copolymer of styrene-acrylic acid-acrylic acid ester (number average molecular weight 16,000 hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 70%, acid value 120, cloud point pH 6) and anthraquinone red fine particles The pigments are each 5.0% by weight solid content,
An electrodeposition dispersion containing 2% by weight of calcium carbonate (pH
7.9, volume resistivity 2 × 10 ² Ω · cm). Using an electrodeposition apparatus having a three-pole arrangement common in the electrochemical field,
The electrodeposited substrate is immersed in an electrodeposition liquid so that the selected TFT corresponding to the red pixel of the final color filter is turned on, and the selected pixel electrode is used as a working electrode, and a saturated calomel electrode is used. The voltage was applied for 3 seconds so that the voltage became 2.7 V. A red colored film was formed on the selected pixel electrode. Thereafter, cascade cleaning was sufficiently performed with a pH-adjusted liquid having a pH value of 6.5.

An electrodeposition solution similar to the above-described electrodeposition solution for a red filter was prepared, except that an ultrafine particle pigment of phthalocyanine green was used as a pigment, a green colored film was formed under the same conditions, and washing was performed similarly. Was.

An electrodeposition solution similar to the above-described electrodeposition solution for a red filter was prepared, except that an ultrafine particle pigment of phthalocyanine blue was used as a pigment, a blue colored film was formed under the same conditions, and washing was performed in the same manner. Was.

Next, the electrodeposited substrate on which the filter portion was formed was subjected to a heat treatment at 230 ° C. for 30 minutes to further harden the film. After that, ITO is deposited on this surface by a sputtering film forming method, and then, by a photolithographic method,
Only the portion corresponding to the color filter was removed and removed, and a transparent display electrode portion was formed in the upper layer portion of the color filter portion. Next, a conductive path between the display electrode portion and the ITO film as a lower pixel electrode was secured. Through the above steps, a color filter integrated with a TFT drive circuit was completed.

This color filter has a pencil hardness of 3H.
In a solvent such as acetone, IPA, N-methylpyrrolidone
There was no change in the film even after immersion for 0 minutes, and the film was durable.

Example 9 An electrodeposited substrate was produced in the same manner as in Example 1 except that the thickness of the glass substrate was 0.7 mm. Next, a styrene-acrylic acid random copolymer (molecular weight 14,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 73%, acid value 90, glass transition point 45 ° C.,
A flow start point of 90 ° C., a decomposition point of 247 ° C., a cloud point of pH 5.8) and an azo red ultrafine particle pigment are dispersed at a solid content ratio of 5: 5 in an aqueous dispersion having a solid content concentration of 8% by weight. Dimethylaminoethanol was mixed to a concentration of 210 mmol / liter. Next, 2% by weight of magnesium phosphate was mixed and stirred into this solution, and an electrodeposition solution (pH 7.9, volume resistance value 2 × 10 ² Ω ·
cm). The electrodeposited substrate is immersed in an electrodeposition solution using an electrodeposition apparatus having a triode arrangement commonly used in the electrochemical field, and the selected TFT corresponding to the red pixel of the final color filter is turned on. With the selected pixel electrode as the working electrode and the saturated calomel electrode
A voltage was applied for 4.5 seconds to 2.5 V. A red colored film was formed on the selected pixel electrode.

Next, the same procedure as in the electrodeposition solution for red filter was carried out except that the azo red ultrafine particle pigment was replaced with a phthalocyanine green ultrafine particle pigment, and that the amount of dimethylaminoethanol was adjusted to 200 mmol / liter. Electrodeposition solution for green filter (pH 7.9, volume resistivity 2 × 10 ² Ω ・
cm). The above voltage was applied at 2.8 V for 3 seconds. A green colored film was formed on the selected pixel electrode. Thereafter, cascade cleaning was sufficiently performed with a pH adjusted liquid having a pH value of 4.2.

Next, the same procedure as in the electrodeposition solution for red filter was carried out except that the azo red ultrafine particle pigment was replaced with a phthalocyanine blue ultrafine particle pigment, and that the amount of dimethylaminoethanol was 190 mmol / liter. Electrodeposition solution for blue filter (pH 7.9, volume resistivity 2 × 10 ² Ω · c
m) was prepared. The above voltage was applied at 2.5 V for 5 seconds. A blue colored film was formed on the selected pixel electrode. Thereafter, cascade cleaning was sufficiently performed with a pH adjusted liquid having a pH value of 4.2.

Next, carbon black black pigment particles (having a carboxyl group on the surface) having an average particle diameter of 13 nm were added in an amount of 5% by weight based on the total weight of the liquid and a photosensitive polymer material (trade name, manufactured by Nogawa Chemical Co., Ltd.) : Diabond) The entirety of the electrodeposited substrate having the colored film formed thereon was immersed in a dispersion solution in which 0.8% by weight and the balance of pure water were ultrasonically dispersed. Thereafter, pattern exposure was performed, and a black film was deposited on conductive portions other than the portion corresponding to the colored filter film. A black matrix / protective layer of a 0.6 μm thick insulating carbon black particle thin film was formed. The optical transmission density of this black matrix film was 2.2.

Next, the electrodeposited substrate on which the filter section was formed was placed in a heating oven at 220 ° C. and left for 1 hour to harden the electrodeposited film and remove the pH adjuster. Thereafter, ITO was deposited on this surface by a sputtering film forming method, and then removed by photolithography except for a portion corresponding to the color filter, and a transparent display electrode portion was formed on the upper layer portion of the color filter portion. . Next, a conductive path between the display electrode portion and the ITO film as a lower pixel electrode was secured. Through the above steps, a color filter integrated with a TFT drive circuit was completed.

When the optical characteristics of the boundary between the filter portion and the black matrix portion were evaluated, the deviation of the edge portion of the boundary was realized with a high accuracy of 3.6 μm or less.

Example 10 A transparent conductive film of ITO having a thickness of 0.1 μm was formed on a non-alkali glass substrate having a thickness of 0.5 mm by a sputtering method.
TiO ₂ with a thickness of 0.1 μm is formed by the sol-gel method,
Heating for one minute. Next, in order to improve the photocurrent characteristics of TiO ₂ , annealing was performed at 360 ° C. for 20 minutes in pure nitrogen gas mixed with 5% hydrogen gas as a reduction treatment, thereby producing an electrodeposited substrate. Styrene-acrylic acid random copolymer (molecular weight 22,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 70%,
Acid value 100, glass transition point 55 ° C, flow start point 94 ° C, decomposition point 2
54 ° C, cloud point pH 5.9) and carbon black (pH value 2.5,
An ultrafine pigment having an average particle diameter of 21 nm and an oil absorption (DPB) of 110 cc / 100 g) was dispersed at a solid content ratio of 3 to 7 to prepare an aqueous dispersion having a solid concentration of 6% by weight. A 10% by weight dioxane dispersion was mixed with stirring so that the concentration became 5% by weight to prepare an electrodeposition solution (pH 8.1, volume resistance value 2 × 10 ² Ω · cm).

Using an electrodeposition apparatus having a tripolar arrangement commonly used in the electrochemical field, the above electrodeposited substrate is immersed in an electrodeposition liquid,
Then, a TiO ₂ electrode was used as a work electrode for the saturated calomel electrode, and a bias potential of 1.7 V was applied to the work electrode. Mercury xenon lamp (Yamashita Denso, wavelength 36
When the light was irradiated for 2 seconds at a light intensity of 5 nm at 50 mW / cm ² ), only the area where the transmitted light was irradiated on the TiO ₂ surface was 1.2 mm.
A black pattern having a thickness of μm was formed. Then the pH value
The cascade cleaning was sufficiently performed with the pH adjusted liquid of 4.5. As a result, a black matrix film having a uniform layer was formed. The optical transmission density of this black matrix film is 2.6
Met.

Next, a styrene-acrylic acid copolymer (molecular weight 14,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 73%,
Acid value 89, glass transition point 42 ° C, flow start point 97 ° C, decomposition point 23
8 ° C, cloud point pH 6.3) and an aqueous dispersion of 6% by weight of solid content in which an azo red ultrafine particle pigment is dispersed at a solid content ratio of 6: 4, and 10% by weight of calcium phosphate %
The dioxane dispersion was mixed with stirring so that the concentration became 5% by weight, and the electrodeposition solution (pH 8.1, volume resistance value 2 × 10 ² Ω)
Cm). Electrodeposition was performed in the same manner as in the formation of the black matrix except that the voltage was 1.8 V and the light irradiation time was 6 seconds. As a result, a red colored film was formed only in the light-irradiated region of the TiO ₂ surface. . Thereafter, the substrate was washed with a pH adjusting liquid having a pH value of 4.8.

An aqueous dispersion having a solid content of 6% by weight was prepared by dispersing the copolymer used in the electrodeposition solution for the red filter and the phthalocyanine green-based ultrafine pigment at a solid content ratio of 6: 4. A 10% by weight dioxane dispersion of calcium phosphate was mixed with stirring to a concentration of 5% by weight to prepare an electrodeposition solution (pH 8.1, volume resistance value 2 × 10 ² Ω · cm). Except that the voltage is 1.8V and the light irradiation time is 7 seconds,
When electrodeposition was performed in the same manner as in the formation of the black matrix, a green colored film was formed only in the region of the TiO ₂ surface irradiated with light. Thereafter, the plate was washed with a pH adjusting liquid having a pH value of 4.7.

An aqueous dispersion having a solid content of 6% by weight was prepared by dispersing the copolymer used in the electrodeposition solution for the red filter and the phthalocyanine blue-based ultrafine pigment at a solid content ratio of 6: 4. Then, a 10% by weight calcium phosphate dioxane dispersion is mixed with stirring so that the concentration becomes 5% by weight, and an electrodeposition solution (pH 8.1, volume resistance value 2 × 10 ² Ω · cm)
Was prepared. Electrodeposition was performed in the same manner as in the formation of the black matrix except that the voltage was set to 1.9 V and the light irradiation time was set to 7 seconds. As a result, a blue colored film was formed only in the light-irradiated region of the TiO ₂ surface. Was done. Thereafter, the substrate was washed with a pH adjusting liquid having a pH value of 4.2.

Thereafter, the electrodeposited substrate on which the filter portion was formed was heat-treated in a heating oven at 190 ° C. to complete the hardening treatment of the electrodeposited film. This film was subjected to a 2H pencil scratch test, which demonstrated that it was a hard film that did not cause scratches. On top of this, a protective layer was coated to produce a color filter.

Example 11 An electrodeposited substrate was produced in the same manner as in Example 1. Next, a mixed solvent in which n-hexadecane and carbon tetrachloride were mixed at a ratio of 4: 1 (volume ratio) was filtered through a microfilter, and then 8-
Bromooctyltrichlorosilane [8-Br (CH ₂ ) ₈ SiCl ₃ ]
Was dissolved in this mixed solvent. Then, a solution having a content of 8-bromooctyltrichlorosilane of 10 ⁻³ mol / l was prepared. The electrodeposited substrate was immersed in this solution for 2 hours. Next, the electrodeposited substrate was washed with n-hexadecane and acetone, air-dried in a nitrogen atmosphere for 30 minutes, and then heated at 80 ° C. for 30 minutes. In order to confirm whether or not the 8-bromooctyltrichlorosilane has bound to the surface of the substrate, Fourier transform infrared absorption spectrum measurement (hereinafter may be referred to as “FT-IR measurement”; Perkin Elmer: System 200 ) And X-ray photoelectron spectroscopy (hereinafter `` XPS measurement '')
It may be called. VG: ESCALAB-220i). As a result of the FT-IR measurement, a signal of symmetric stretching vibration and antisymmetric stretching vibration of -CH ₂ -group at 2840 to 2930 cm ^-1 is 1240 cm.
^-1 near the stretching vibration of the Si-C group, near 1080cm ^-1 Si-O-Si
The skeletal vibrations of the groups were each observed. As a result of XPS measurement, 7
Signals from 3d near 0 eV, 3p near 180 eV, and 3s near 256 eV were observed from Br atoms. At the same time, no signal from Cl atoms was observed, confirming that dehydrochlorination had occurred. From the above, it was confirmed that 8-bromooctyltrichlorosilane was bonded to the substrate.

Next, a copolymer of styrene-acrylic acid-acrylate (number average molecular weight 16,000 hydrophobic groups /
(Hydrophilic group + hydrophobic group) molar ratio 70%, acid value 120, cloud point pH
) And an anthraquinone-based red fine particle pigment, each having a solid content of 5.0% by weight, and further containing 0.5% by weight of tetramethoxysilane as a curing agent (pH 7.
9, volume resistance value 2 × 10 ² Ω · cm). The electrodeposited substrate is immersed in an electrodeposition solution using an electrodeposition apparatus having a triode arrangement commonly used in the electrochemical field, and the selected TFT corresponding to the red pixel of the final color filter is turned on. And the selected pixel electrode as a working electrode,
A voltage was applied to the saturated calomel electrode so that the voltage became 2.7 V for 3 seconds. A red colored film was formed on the selected pixel electrode. Next, unnecessary adhesion electrodeposition liquid was washed away using washing water having a pH value of 6.5 to complete a red filter portion.

Similarly, an electrodeposition solution similar to the above-mentioned electrodeposition solution for a red filter was prepared and electrodeposited under the same conditions except that an ultrafine particle pigment of phthalocyanine green was used as a pigment. Was formed. Next, pH value 6.5
Unnecessary electrodeposition liquid was washed away using the washing water of No. 1 to complete a green filter portion.

Similarly, an electrodeposition solution similar to the above-mentioned electrodeposition solution for a red filter was prepared except that an ultrafine particle pigment of phthalocyanine blue was used as a pigment, and electrodeposition was performed under the same conditions. Was formed. Next, unnecessary adhesion electrodeposition liquid was washed away using washing water having a pH value of 6.5 to complete a blue filter portion.

Next, the electrodeposited substrate on which the filter portion was formed as described above was subjected to a heat treatment at 230 ° C. for 30 minutes to further harden the film. Thereafter, ITO was deposited on this surface by a sputtering film forming method, and then removed by photolithography except for a portion corresponding to the color filter, and a transparent display electrode portion was formed on the upper layer portion of the color filter portion. . Next, a conductive path between the display electrode portion and the ITO film as a lower pixel electrode was secured. Through the above steps, a color filter integrated with a TFT drive circuit was completed. This color filter film has a pencil hardness of 3
When immersed in a solvent such as acetone, IPA, N-methylpyrrolidone, etc. for 10 minutes at H, the film had no change and was durable.

[0126]

The electrodeposition liquid of the present invention can be efficiently applied to the electrodeposited substrate in response to a change in pH of the aqueous solution near the electrodeposited substrate even when a relatively low potential voltage is applied to the electrodeposited substrate. Is deposited, and once formed, it is possible to form a robust electrodeposition cured film in which the polymer material is not easily eluted.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G09F 9/00 313 G09F 9/00 313 (72) Inventor Katsuhiro Sato 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Xerox (72) Inventor Katsumi Nukata 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. Person Takao Tomino 430 Green Tech Nakai, Nakai-cho, Ashigagami-gun, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. 430 Gree, Nakaicho, Ashigara-gun, Kanagawa Tek Naka F-term in Fuji Xerox Co., Ltd. (reference) 2H048 BA11 BA47 BA62 BB47 4D075 BB89Z DA06 DB14 DC22 EA05 EB22 EB42 EB45 EC08 4J038 CG031 CG061 CG071 CG081 CG141 CG171 CH121 DA042 DA142 GA162 GA03 GA04 AA17 BB12 GG11 HH20 LL14

Claims (15)

[Claims] 1. An electrodeposition solution containing an anionic polymer whose solubility or dispersibility in an aqueous liquid rapidly changes due to a change in pH, and a curing agent for the anionic polymer. 2. The method according to claim 1, wherein the change in solubility or dispersibility is pH.
2. The electrodeposition liquid according to claim 1, wherein the liquid is generated within the range 2. 3. The method according to claim 1, wherein the curing agent is at least one thermosetting resin selected from the group consisting of a phenol resin, a urea resin and a melamine resin.
The electrodeposition liquid according to the above. 4. The electrodeposition liquid according to claim 1, wherein the curing agent is at least one compound selected from a polyvalent epoxy compound and a polyvalent isocyanate compound. 5. The electrodeposition solution according to claim 1, wherein the curing agent is at least one metal compound selected from the group consisting of a metal alkoxide compound and a polyvalent metal salt. 6. The method according to claim 1, wherein the anionic polymer exhibits a cloud point (turbid point) in a pH range of 5.5 to 6.5 under the condition that the solid content concentration in water is 1% by weight or less. The electrodeposition liquid according to claim 5. 7. An electrodeposition solution for producing a color filter, characterized in that a colorant is further added to the electrodeposition solution according to any one of claims 1 to 6. 8. An electrodeposition liquid containing an anionic polymer, a curing agent of an anionic polymer, and an adhesion improver, whose solubility or dispersibility in an aqueous liquid changes drastically as the pH changes. 9. An electrodeposited substrate is brought into contact with the electrodeposited liquid according to any one of claims 1 to 8, and a pH value in the vicinity of the electrodeposited substrate is changed, so that the electrodeposited substrate is exposed on the electrodeposited substrate. A method for producing an electrodeposited cured film, comprising: depositing an electrodeposited film on a substrate, and thereafter curing the electrodeposited film. 10. The electrodeposited substrate is brought into contact with an electrodeposition solution containing an anionic polymer whose solubility or dispersibility in an aqueous liquid rapidly changes due to a change in pH, and the pH value near the electrodeposited substrate is adjusted. A method for producing an electrodeposited cured film, comprising: depositing an electrodeposited film on the electrodeposited substrate by changing the thickness of the electrodeposited substrate, then contacting the electrodeposited film with a curing agent, and then curing the electrodeposited film. 11. An electrodeposited cured film produced by the method according to claim 9. 12. An electrodeposited cured film produced by the production method according to claim 10. 13. The electrodeposited cured film according to claim 11, wherein the electrodeposited cured film is adhered to the electrodeposited substrate via an adhesive material layer. 14. The electrodeposition cured film according to claim 13, wherein the adhesive material layer is made of an adhesive material having a functional group capable of chemically bonding to both the electrodeposition film and the electrodeposition substrate. 15. An electronic device comprising the electrodeposition cured film according to claim 11 as an optical filter.