JPH11125813A - Production of color filter for liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color filter having good color characteristics in which the color characteristics of coloring pigments are not decreased and which prevents decrease in the film strength and does not decrease the transmittance and reflectance, as well. SOLUTION: A pattern electrode 4 is dipped in a treating liquid prepared by dissolving a color pigment or dispersing the pigment as fine particles to electrolytically reduce a surfactant near the electrode 1 exposed as a pattern. Thereby, the soluble state of the soln. or the dispersion state of the dispersion liquid is broken to make the color pigment deposit on the electrode 1. A transparent resin is impregnated in the deposited color pigment, as well. Further, after the electrode on which the film of a color pigment pattern is formed is adhered to a substrate through a transparent adhesive, only the electrode is peeled to transfer only the pattern of the color pigment to the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter used for a liquid crystal display device and the like, and more particularly to a method of electrochemically manufacturing a color filter.

[0002]

2. Description of the Related Art Generally, a color filter for an electronic device such as a liquid crystal display device or an image pickup device is formed by forming a black matrix at a predetermined position on a transparent substrate, and then forming a red (Red), green (Green), Blue (Blu
e) The color filter layer is formed in a pixel shape.

[0003] In view of the light resistance and heat resistance of the color filter, methods for manufacturing a color filter using a pigment as a pigment include a pigment dispersion method, a printing method, and an electrochemical method. In these color filter manufacturing methods, coating liquids, inks, processing liquids, and the like in which a pigment is dissolved or dispersed as fine particles in an organic solvent solution of a binder resin or an aqueous solution are widely used. The binder resin is used as a means for dispersing the pigment in the solution, a means for preventing the dispersed pigment particles from aggregating, and a means for fixing the formed pigment particles on the substrate.

As a method of dispersing a pigment into a solution using a binder resin, there are methods such as a ball mill and a sand mill. In these methods, the pigment is finely divided into primary particles or a state close to primary particles. It is difficult. Therefore, the color characteristics of the obtained color filter are reduced from those of the pigment.

[0005] When a coating liquid, ink, treatment liquid or the like using a binder resin is used as described above, pigment particles and the binder resin coexist in the formed thin film. As a result, the color characteristics of the obtained color filter are lower than those of a thin film color filter composed of only pigment particles. In addition, since the formed thin film is composed of only the pigment, the film strength and adhesion strength of the pigment may be reduced depending on the type of the pigment, the film forming conditions, and the like.

[0006] In the electrochemical method, a transparent electrode such as ITO is provided on a transparent substrate, and a pigment or the like is attached thereto. However, this reduces the transmittance as a display device. Further, for example, when a reflective color filter is produced by an electrochemical method as disclosed in Japanese Patent Application Laid-Open No. H7-62594, a metal or metal oxide substrate is used instead of a transparent substrate to obtain a light-reflective color filter. When the substrate is used, the surface of the substrate is partially ionized and dissolved, which reduces the reflectance of the display device.

[0007]

SUMMARY OF THE INVENTION The present invention provides a pigment thin film in which the pigment is finely divided to primary particles or a state close to the primary particles, whereby the color characteristics of the pigment are not reduced. An object of the present invention is to provide a good color filter for a liquid crystal display device. Another object of the present invention is to provide a color filter for a liquid crystal display device having good color characteristics in which the color characteristics of a pigment are not reduced by forming a pigment thin film in which a binder resin does not coexist. Also,
The present invention provides a color filter for a liquid crystal display device in which a decrease in film strength or adhesion strength is prevented. Further, the present invention provides a color filter for a liquid crystal display device which does not decrease transmittance as a display device, and a color filter for a reflection type liquid crystal display device which does not decrease reflectance as a display device.

[0008]

The present invention has been made to solve the above-mentioned problems, and the invention of claim 1 of the present invention provides (1) a method in which a metal or metal oxide electrode which is more base than a surfactant is formed on the electrode. Providing a photoresist layer, (2) exposing and developing a pattern of a predetermined color on the photoresist layer to form a pattern, and exposing the electrode in a pattern. (3) electrolytic reduction on the electrode surface. The surface active agent, and a treatment liquid in which an organic or inorganic coloring pigment is dissolved or dispersed as fine particles, by immersing the metal electrode and the electrode that are more noble than the electrode in an electrically connected state, the exposed (4) a step in which the surfactant in the vicinity of the electrode is electrolytically destroyed and the coloring pigment is attached to the exposed electrode;
A step of applying a transparent resin on the colored pigment adhering to the exposed electrode and drying it, and impregnating the colored pigment with the transparent resin; (5) repeating the above steps (2) to (4) for each color sequentially (6) removing the remaining photoresist layer, (6) applying the color pigment pattern obtained by the steps (1) to (5) to the electrode via a transparent adhesive. A method of manufacturing a color filter for a liquid crystal display device, comprising the steps of: adhering to a transparent substrate with the substrate inside, and peeling off only the electrode to transfer only the color pigment pattern to the transparent substrate.

According to a second aspect of the present invention, in the color filter for a liquid crystal display device according to the first aspect, the surfactant contains an aromatic azo compound residue in a hydrophobic portion thereof. It is a manufacturing method of.

The invention according to claim 3 of the present invention is characterized in that the solvent is water or a mixed solvent of water and an organic solvent compatible with water. This is a method for manufacturing a color filter for a liquid crystal display device.

According to a fourth aspect of the present invention, in the color for a liquid crystal display device according to the first, second or third aspect, the coloring pigment is hydrophobic or weakly hydrophilic. This is a method for manufacturing a filter.

The invention according to claim 5 of the present invention is characterized in that the transparent substrate is a light-reflective metal or metal oxide substrate or a substrate provided with a light-reflective metal or metal oxide thin film. A method for manufacturing a color filter for a liquid crystal display device according to any one of claims 1 to 4.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for manufacturing a color filter for a liquid crystal display device according to the present invention will be described in detail based on an embodiment. In FIG. 1, the metal or metal oxide electrode (1) which is lower than the surfactant used in the present invention serves as a temporary support for the color pigment pattern, and is lower than the surfactant, or It can be in a low state,
Those having sufficient strength, flatness and heat resistance are preferable.
Further, an electrode which is easily bent so that the electrode as a temporary support of the pattern of the color pigment in the transfer step is easily peeled off is also preferable. A base metal is a low-potential metal,
For example, Al, Zn, Cr, Fe, Co, Ni and the like can be mentioned, and the standard electrode potential is about -2.0 to + 0.5V. From the base metals, an appropriate one is selected according to the conditions such as a surfactant, a solvent, and an electrolyte to be used. Al has a low electrode potential, is relatively stable, is inexpensive, and is suitable.

When these materials are used, a plate-like material may be used as it is, or a thin film may be formed on an appropriate substrate or a film and used as a temporary support for a pattern of a colored pigment. 2 (a) and 2 (b) show another example of a substrate or a film serving as a temporary support. As shown in FIG. Metal or metal oxide thin film (14)
May be provided as an electrode to form a pattern of a colored pigment, or as shown in FIG. 2B, a metal or metal oxide thin film such as ITO, which is nobler than a surfactant, is formed on a substrate or a film (15). For example, a transparent thin film (16) such as the above may be used as an electrode to form a pattern of a colored pigment.

As a method of forming a thin film, a sputtering method, a vapor deposition method, a CVD method, various coating methods, a pyrosol method, and the like are employed, but the method is not particularly limited thereto. From the viewpoints of film thickness, film thickness uniformity, film composition uniformity, and film surface flatness, a sputtering method, a vapor deposition method, a CVD method, and the like are preferable. In order to enhance the flatness of the surface of the color filter after transfer, the surface of the plate or the thin film is preferably high in flatness and more preferably close to a mirror state.

In order to use a metal or metal oxide which is more noble than a surfactant as the electrode (1), a thin film is formed on a plate or on a substrate or film using these electrode materials. Then, as shown in FIG. 8, when the electrodes are immersed in the treatment liquid (40), a metal that is lower than the electrodes and a surfactant and has a lower standard electrode potential, and functions as an anode during electrolytic reduction, or By immersing the metal oxide in an electrically connected state, the coloring pigment selectively adheres to the electrode surface which is an electrode material which is nobler than the surfactant.

Examples of the noble electrode material that functions as a cathode include metals such as Ag, Pd, and Pt. Ag is inexpensive and suitable. On the other hand, the material of the base electrode (30) functioning as an anode is, for example, Al, Mn, Zn, Cr, Fe, Co, Ni, P
b, Sn, Cu and the like. Standard electrode potential is-
About 2.0 to +0.5 V, a surfactant to be used,
Appropriate ones should be selected according to the conditions such as the solvent and the electrolyte. Al has a low electrode potential, is relatively stable, is inexpensive, and is suitable. In addition, there is no limitation on the shape of the anode electrode, various shapes such as a plate shape, a rod shape, a spherical shape,
And an appropriate thin film formed on the substrate can be selected.

In FIG. 1, when a transmission type color filter is manufactured, a substrate (2) to which a pattern of a color pigment is transferred has sufficient strength, flatness, heat resistance, light transmittance and the like. Those having sufficient adhesive strength with the adhesive are preferred.
For example, transparent glass or plastic which is usually used as a color filter substrate may be used.
Those having a light transmittance of 90% or more in the visible wavelength region are preferred. As for the heat resistance, it is more preferable that no discoloration or deformation is observed at a temperature of up to 150 ° C. and that there is no various deterioration at a temperature of up to 200 ° C.

The heat resistance varies depending on the heat treatment temperature required for film formation, the heat treatment temperature of the pigment, the heat treatment temperature in the liquid crystal panel forming step, and the like, but glass is generally preferred. Further, as the composition of the glass, a low-alkali, non-alkali glass containing few alkali metal ions, which causes deterioration of the display characteristics of the display device, is preferable.

When manufacturing a reflection type color filter (70) as shown in FIG. 3, the substrate (12) to which the pattern of the color pigment is transferred has sufficient strength, flatness, heat resistance, A metal or a metal oxide having a sufficient adhesive force with an adhesive and having high light reflectivity in a visible wavelength region can be used as the light reflective substrate (12). For example, for metals, Al, Cr, Ni, P
t, Ag and the like. Al and Ag have high light reflectivity in the visible wavelength range and are inexpensive and suitable.

The light reflectance is preferably 85% or more on average in the visible wavelength range. When these materials are used, a plate-like material may be used as it is as shown in FIG. 3A, or a light-reflective thin film (A) may be formed on an appropriate substrate (22) as shown in FIG. 32) may be formed and used as a light-reflective substrate.

Light-reflective substrate (12) as is
When used as a metal material, the metal material has sufficient strength, flatness, heat resistance, and high light reflectivity.
Has a low specific gravity, so that it is light and suitable even with a thickness that provides sufficient strength. The thickness of the light-reflective substrate (12) depends on the form of the display device to be used.
About 1 to 1.5 mm is preferable.

When a light-reflective thin film (32) is formed on a suitable substrate (22) and used as a light-reflective substrate, the light-reflective thin film (32) has sufficient light-reflecting properties. As long as it is possible, 5000 ° or more is preferable. As a method of forming a thin film, a sputtering method, a vapor deposition method, a CVD method, various coating methods, a pyrosol method, and the like are employed, but the method is not particularly limited thereto. From the viewpoints of film thickness, film thickness uniformity, film composition uniformity, and film surface flatness, a sputtering method, a vapor deposition method, a CVD method, and the like are preferable.

The photoresist which can be used in the present invention is preferably a positive type photoresist, and is a photo-soluble resist in which a portion exposed to ultraviolet light, visible light, electron beam or the like is eluted by a developer and contains the above-mentioned surfactant. There is no particular limitation as long as it is not affected by the processing liquid. For example, as a positive photoresist, a photosensitive resin composition containing a diazonium salt and a paraformaldehyde condensation polymer, a photosensitive resin composition containing orthoquinonediazides or orthodiazooxides, and an alkali-soluble azide polymer are included. Reaction to an acid, comprising a photosensitive resin composition, a photosensitive resin composition containing an azide compound developable with water or an aqueous alkali solution, and tertiary butyl ester of carboxylic acid or tertiary butyl carbonate of phenol. Examples include a positive photosensitive resin composition containing a polymer having a highly functional polyfunctional group and a photopolymerization initiator (such as an onium salt) that generates an acid upon exposure.

The composition of these positive photoresists may be adjusted according to exposure conditions, development conditions, and the like, and used alone or in combination of two or more. The organic solvent for dissolving or dispersing the positive photoresist is not particularly limited as long as it can dissolve the resin and the resin composition, for example, various glycol ethers, ketones, ethers, alcohols, Isopropanols,
Examples include hydrocarbons, esters, acid amides and the like. These organic solvents may be used alone or in combination of two or more.

The surfactant which can be used in the present invention includes a surfactant comprising a hydrophobic part and a hydrophilic part, and a surfactant comprising a hydrophobic part and a hydrophilic part, wherein the hydrophobic part is an aromatic azo compound residue. Is a surfactant containing a group, solubilizes hydrophobic or weakly hydrophilic organic or inorganic pigments in water or a mixed solvent of water and an organic solvent compatible with water, or dispersed as fine particles. It has the ability and can be electrolytically reduced at the electrode (1) functioning as a cathode electrode. More specifically, for example, Japanese Patent Application Laid-Open No. 7-2383
82 and azo compounds disclosed in JP-A-7-292478. One type may be used alone, or two or more types may be used in combination.

The solvent which can be used in the present invention is water or a mixed solvent of water and an organic solvent which is compatible with water. However, the solvent is not limited thereto, and a pH adjuster for adjusting pH is not limited thereto. As long as it can be dissolved, an organic solvent alone may be used. As the organic solvent, for example, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, propylene carbonate and the like are suitable.

In the present invention, when the surfactant is electrolytically reduced in a solvent, a pH adjuster may be added to adjust the pH. For example, lithium salts such as lithium sulfate, lithium acetate, lithium nitrate, lithium bromide and lithium perchlorate; sodium salts such as sodium sulfate, sodium acetate and sodium chloride; potassium salts such as potassium sulfate, potassium acetate and potassium bromide And inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and citric acid.

The hydrophobic or weakly hydrophilic organic or inorganic pigments usable in the present invention include organic pigments such as azo lake type, insoluble azo type, phthalocyanine type, quinacdrine type, dioxazine type, isoindoline type and isoindolinone. And verinone-based, anthraquinone-based, perylene-based, quinophthalene-based, thioindigo-based, diketopyrrolopyrrole-based compounds, and mixtures thereof, and inorganic pigments such as carbon black.

Fluorescent whitening dyes such as 1,2-bis (benzoxazolyl) ethylene derivatives, 1,2-bis (benzoxazolyl) coumarin derivatives, 4-methoxy-N-methylnaphthalimide, -Methyl-5- [4
-(3-ethyl-2-benzothiazolylidene) -2-hexenylidene] rhodanin derivatives, such as rhodanine;
Coumarin derivatives such as trifluoromethyl-7-dimethylaminocoumarin, 4- (dicyanomethylene) -2-
Methyl-6- (p-dimethylaminostyryl) -4H-
Laser dyes such as pyran may be used.

The treatment liquid used in the present invention is adjusted in water or a mixed solvent of water and an organic solvent compatible with water.
It is carried out by grinding or grinding a hydrophobic or weakly hydrophilic organic or inorganic coloring pigment in the presence of the surfactant. For grinding and grinding, a dispersion device such as a sand mill, a ball mill, an ultrasonic homogenizer, and a paint conditioner can be used. It is preferable that the particle size of the color pigment is reduced to 0.1 μm or less primary particles or a state close to the primary particles.

When several kinds of color pigments are used, they may be all mixed and stirred beforehand and then dispersed using a dispersing apparatus. However, each type is separately dispersed, finely divided, and then dispersed. The liquids may be mixed with each other, and then the liquid may be further dispersed. When the liquids are mixed after they are separately dispersed, it is preferable to perform the mixing in a state in which the mixing ratio, the concentration, the temperature, and the like of the liquids are close to each other, since the change in the dispersed state is small.

As shown in FIG. 1A, a photoresist layer (3) is formed on the electrode (1) functioning as a cathode electrode.
Then, as shown in FIG. 1 (b), for example, UV light irradiation (9) is performed, and the photoresist layer (3) is removed in a desired pattern by subsequent development, as shown in FIG. 1 (c) and FIG. As shown in FIG. 4, a pattern electrode (4) is formed.

As shown in FIG. 8, the pattern electrode (4) is electrically connected to the metal electrode (30) by the connection portion (50), and the pattern electrode (4) and the metal electrode (3) are connected.
0) is immersed in the treatment liquid (40), so that in the vicinity of the pattern portion where the electrode (1) is exposed,
The surfactant is electrolytically reduced without using an external power supply, and a coloring pigment is attached to the surface of the electrode (1). FIG. 1
(D) and as shown in FIG. 5, for example, a red pixel (5R)
Is formed.

When the pattern electrode (4) is immersed in the treatment liquid, the film formation can be promoted by heating the treatment liquid within a range in which the solvent does not evaporate or volatilize.

Further, since the thin film formed in the present invention is composed of only the color pigment, the type of the color pigment,
Depending on the film forming conditions and the like, the film strength and adhesion strength of the color pigment may be reduced, and furthermore, if the color pigment is made porous and the film formation for the second and subsequent colors is continued, color mixing may occur. As one method for preventing these, there is a method of baking the particles by heating the film to 100 ° C. to 200 ° C. after the formation of the first color. In the present invention, after the formation of the first color, a photo-curable or thermo-curable transparent resin liquid is applied, and the transparent resin is impregnated into a thin film formed of a colored pigment, thereby obtaining film strength and adhesion to a substrate. This is a method that reinforces the force and hides the electrode.

The coating liquid, ink, treatment liquid, and the like used in other color filter manufacturing methods using a coloring pigment as a pigment, such as a pigment dispersion method, a printing method, and an electrochemical method, may be prepared by adding a coloring pigment to an organic solvent solution of a binder resin. Since it is dissolved or dispersed as fine particles in an aqueous solution or in an aqueous solution, the properties required for the binder resin include the dispersibility of the color pigment in the solution, the anti-aggregation property of the color pigment particles, and the coloring on the substrate. For example, the fixability of pigment particles.

In the present invention, since the transparent resin is impregnated in a thin film formed of a color pigment, the material of the transparent resin is not restricted by the above-described properties such as dispersibility and anti-aggregation properties. Can be selected. For example, heat resistance, since excellent materials such as transparency can be selected, the color characteristics of the color filter obtained even when a transparent resin coexists with the color pigment, the performance of the color characteristics of the color pigment is less reduced The color filter has good color characteristics.

In the present invention, the photo-curable or thermo-curable transparent resin which can be used is a curable resist having high transparency and curable by ultraviolet rays, visible rays, electron beams, heat or the like. There is no particular limitation as long as it is not affected by the processing solution containing a surfactant. For example, acrylic or ester-based, polyimide-based, cyclized rubber-based, siloxane-based, epoxy-based polymers or copolymers, specifically, acrylic resins, acrylic acid, methacrylic acid, methyl Acrylate or alkyl methacrylate such as acrylate or methyl methacrylate, cyclic acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, or an epoxy or siloxane group, or an acrylic acid or methacrylic acid derivative into which a polyimide precursor is introduced. Examples of the resin include a resin synthesized with a molecular weight of about 5 × 10 ^{3 to} 100 × 10 ³ by using more than one kind of monomer.

The photopolymerizable monomers include diacrylates as bifunctional monomers, triacrylates as trifunctional monomers, and tetraacrylates, penta and hexaacrylates as polyfunctional monomers. As the photoinitiator, triazine, acetophenone, benzyne, benzophenone, thioxanthone and the like are suitable. Further, a crosslinking agent such as a melamine resin may be added to the composition. As the solvent, ketones such as cyclohexanone, glycol ethers such as cellosolve, alcohols such as butanol, esters such as cellosolve acetate, or toluene, xylene,
A single or a mixture of two or more of diclimes and the like can be mentioned, but a strongly polar solvent such as tetrahydrofuran or dimethyl sulfoxide is likely to affect the positive photoresist, and therefore a nonpolar or weakly polar solvent or a weak solvent is used. Solvent compositions are more preferred.

In general, in a liquid crystal display device, the thickness (cell gap) of a liquid crystal layer needs to be uniform for uniform display quality and stable driving of liquid crystal molecules. As a general means of keeping the cell gap constant, a method of distributing beads made of glass or synthetic resin in the liquid crystal layer is used. At this time, if the color filter does not have a certain degree of hardness, beads may sink into the color filter,
Such phenomena as scratching occur and adversely affect display quality.

If the film hardness of this color filter is expressed by a measuring method according to a pencil scratch test of JIS (K5400-1990), the color filter film hardness is 2H or less in pencil hardness and the color filter by beads is used. In the case of 1H or less, beads may be entangled in the color filter at 1H or less, and the film hardness of the color filter is required to be 2H or more in pencil hardness, and 3H or more is more preferable.

The amount of the photopolymerizable monomer is not particularly limited, but is about 20 to 150% by weight of the acrylic resin. The addition amount of the photopolymerization initiator is not particularly limited, but 5 to 50% by weight of the photopolymerizable monomer,
Preferably, 10 to 30% by weight may be used by adding one or two kinds. The solid content ratio is 2% to 40% by weight, preferably 3% to 2% by weight based on 100% by weight of the resin composition.
0% by weight is suitable for impregnation.

The impregnation of the thin film of the color pigment with the above-mentioned photocurable or thermosetting transparent resin composition is carried out by forming a first color film, drying the film, and then placing the film in a bath of the photocurable or thermosetting transparent resin composition. ,
It may be dipped for about 10 seconds to 1 hour, but may be applied by a method such as roll coating or spin coating. Further, immediately after the immersion or application, by reducing the pressure to 10 × 10 ³ Pa to 10 Pa in a state where the resin composition is not dried, the air in the porous structure of the thin film of the coloring pigment is evacuated, and the impregnation is promoted. Can be. The drying may be drying under reduced pressure, but may be heating drying, or may be a combination of heating drying and reduced pressure drying. Further, when spin coating and drying under reduced pressure or drying under reduced pressure are combined, after drying, the coating film of the photocurable or thermosetting transparent resin remaining on the positive photoresist film becomes thinner, which is more preferable.

As shown in FIG. 1D and FIG. 5, for example, a transparent resin is applied to an electrode on which a red pixel (5R) is formed.
By drying and impregnating the transparent resin, a red pixel (6R) impregnated with the transparent resin is formed as shown in FIG. By repeating the steps of FIGS. 1 (b) to (e) for each color, as shown in FIGS. 1 (f) and 6, a red pixel (6R) and a green pixel (6G) ), A mosaic color filter of blue pixels (6B) is formed.

Further, when forming the final color, it is not always necessary to remove all the photoresist layer (3), and a portion which does not affect the post-process such as the production of a liquid crystal panel can be left. For example, as shown in FIG. 1 (g), the photoresist layer (3) is removed between the pixels of each color and around the pixel area, and the remaining photoresist layer (13) is formed at the edge of the pattern electrode (4). Then, if immersed in a black processing solution, a black light shielding portion (7) shown in FIGS. 1 (h) and 7 is formed. The removal of the remaining photoresist layer (13) at the edge of the patterned substrate electrode (4) as shown in FIG. 1 (l) may be performed by a photoetching method, a laser irradiation method, or the like.

As described above, after the color filter composed of the red pixel (6R), the green pixel (6G), the blue pixel (6B) and the black light-shielding portion (7) is formed, the electrode (1) as a temporary support is formed. ) To the substrate (2), a red pixel (6R), a green pixel (6G), a blue pixel (6B), and a black light shielding portion (7).
The adhesive (11) used for transferring the colorant has radiation curability, and after curing, the red pixel (6R) and the green pixel (6).
G) A material that exhibits sufficient adhesiveness and adhesiveness to fix the blue pixel (6B) and the black light-shielding portion (7) on the substrate (2) is used. After curing, a color filter that satisfies the necessary conditions as a color filter such as thermoplasticity, heat resistance, light resistance, and chemical resistance is used.

The adhesive (11) satisfying these conditions is:
A thermoplastic resin, a plasticizer, a radiation curable resin, a tackifier and the like are appropriately mixed. Examples of the thermoplastic resin include polyethylene terephthalate resin, polystyrene resin, acrylic resin, methacrylic resin, butyral resin, polyvinyl butyral resin, polyvinyl acetate resin, polyvinyl chloride resin, urethane resin, and cellulose resin.

Examples of the plasticizer include dibutyl phthalate, dicyclohexyl phthalate, diheptyl phthalate, dioctyl phthalate, polyethylene glycol, polypropylene glycol and the like. Examples of the radiation-curable resin include phenol resin, resorcinol resin, urea resin, melamine resin, unsaturated polyester resin, thermosetting acrylic resin, diallyl phthalate resin, isocyanate resin, polyurethane resin, silicone resin, acrylate diester, and the like. Can be

Incidentally, a primer treatment may be performed to enhance the adhesion between the substrate (2) and the adhesive (11).
As the primer treatment, for example, if glass is used as the substrate, there is a method of treating the glass surface with a silane coupling agent or the like.

In the present invention, the red pixel (6R),
In order to transfer the green pixel (6G), the blue pixel (6B) and the black light-shielding portion (7), the substrate (2) and the adhesive (1
The adhesive strength between the electrode (1), which is a temporary support, and the red pixel (6R), the green pixel (6G), and the blue pixel (6B) with the temporary support.
In addition, it is necessary that the adhesive strength with the black light-shielding portion (7) be sufficiently strong, and an adhesive or a primer treatment that satisfies this condition is selected.

The application of the adhesive (11) to the substrate (2)
For example, methods such as spin coating, spray coating, roll coating, gravure coating, and blade coating are used. If necessary, the viscosity of the adhesive may be adjusted with a solvent or diluent. The thickness of the adhesive should be 1 after coating and drying.
-20 μm is preferred because it has a necessary and sufficient adhesive strength and at the same time has little effect on the transparency of the color filter.

From the electrode (1), which is a temporary support, to the substrate (2)
For the transfer of the red pixel (6R), the green pixel (6G), the blue pixel (6B) and the black light-shielding portion (7), for example, a laminator is used. It is performed by a method such as ordinary lamination, heat lamination, vacuum lamination and the like.

The red pixel (6R) and the green pixel (6R)
G), the blue pixel (6B) and the black light-shielding portion (7) are adhered to the substrate (2) via the adhesive (11), and then the electrode (1) serving as the temporary support is peeled off. 6R), the green pixel (6G), the blue pixel (6B), and the black light-shielding portion (7) are transferred, and subsequently, radiation such as post-exposure, post-bake, or electron beam (EB) irradiation is performed. The black light-shielding portion, the adhesive and the like are cured and fixed to the substrate (2).

As shown in FIG. 1 (N), the above-mentioned red pixel (6R) and green pixel (6G) shown in FIG. 1 (R) are placed on a substrate (2) having a surface coated with an adhesive (11). The electrode (1) on which the blue pixel (6B) and the black light-shielding portion (7) are formed is press-bonded, and for example, an ultraviolet ray (UV) and an electron beam (E
B) or the like, the adhesive is cured to cure the adhesive, and only the electrode (1) is peeled off, so that a red pixel (6R) and a green pixel (6) are formed on the substrate (2) as shown in FIG.
G), a color filter to which a blue pixel (6B) and a black light shielding portion (7) are transferred.

After the transfer to the substrate (2) is completed, if necessary, a transparent protective film (8) may be formed on the film forming surface as shown in FIG. Examples of the material include resins such as polymers or copolymers such as acrylic, ester, polyimide, cyclized rubber, siloxane, and epoxy. Examples of the solvent for these resins include cellosolve compounds, cyclohexanone, methyl isobutyl ketone, diethylene glycol ether, ester compounds, and mixtures thereof.

Further, an initiator, a crosslinking agent and the like may be added to the protective film liquid. The application of the protective film liquid may be performed by a method such as a spin coater, a roll coater, a knife coater, and a gravure coater. After the application, heat treatment or exposure treatment is performed to cure. The transmittance of the protective film is preferably from 0.1 to 3.0 μm in film thickness and 90% or more in the entire visible light region.

Next, the principle of film formation according to the present invention will be described. Using a surfactant containing an aromatic azo compound residue in the hydrophobic part of a surfactant consisting of a hydrophobic part and a hydrophilic part, in water or in a mixed solvent of water and an organic solvent compatible with water and water In a solution in which a hydrophilic or weakly hydrophilic organic or inorganic pigment is dissolved, or in a dispersion liquid dispersed as fine particles, the surfactant is a pigment, the hydrophobic portion inside,
The micelles are formed with the hydrophilic portion facing outward.

In this solution, a photoresist layer (3) is provided on the electrode (1), and only the photoresist layer (3) is removed in a desired pattern to form the pattern exposing the electrode (1). The electrode (4) is connected to a metal electrode (3
When the electrode (1) is immersed in an electrical connection state with the electrode (0), the exposed electrode (1) functions as a cathode electrode, and the surfactant itself near the electrode (1) is electrolytically reduced by the influence of the cathode electrode and decomposed. The formed micelles are destroyed and the pigment adheres to the cathode electrode or electrode (1). The electrode (1) and the metal electrode (30), which is lower than the electrode, are in an electrically connected state. ) Serves as a cathode electrode, and the metal electrode (30), which is more base than the electrode, functions as an anode electrode. The micelle destruction and the adhesion of pigment are selectively performed on the cathode electrode, that is, the electrode (1).

In the present invention, a surfactant is used to cover the color pigment with the hydrophobic part inside and the hydrophilic part outside, so that micelles are formed. To fine particles. Further, only by the destruction of micelles, the primary particles or the coloring pigment finely divided into the primary particles are formed on the electrode (1).

[0061]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.

<Example 1> (Preparation of red dispersion) 1000 ml of 0.1N hydrochloric acid aqueous solution
The surfactant [AZPE, manufactured by Dojin Chemical Co., Ltd.]
G1000] (2.0 g) and 8.9 g of a dianthraquinone-based red pigment were added and stirred, followed by dispersion with an ultrasonic homogenizer [150 W, 20 KHz] for 30 minutes while cooling with water to obtain a red dispersion.

(Preparation of Green Dispersion) To 1,000 ml of a 0.1N aqueous hydrochloric acid solution, 4.5 g of a surfactant (trade name [AZPEG1500] manufactured by Dojindo Co., Ltd.) and 27.8 g of a chromobromocopper phthalocyanine pigment were added. After stirring, while cooling with water, an ultrasonic homogenizer [150 W, 20 KHz
] For 30 minutes to obtain a green dispersion.

(Preparation of Blue Dispersion) To 1,000 ml of a 0.1N aqueous hydrochloric acid solution, 2.0 g of a surfactant {AZPEG1000} (trade name, manufactured by Dojindo Co., Ltd.) and 11.5 g of a copper phthalocyanine blue pigment were added. After stirring, the mixture was cooled with an ultrasonic homogenizer [150W, 20K Hz] while cooling with water.
Dispersion was performed for 0 minutes to obtain a blue dispersion.

(Preparation of Black Dispersion) To 1,000 ml of a 0.1N aqueous hydrochloric acid solution, 6.0 g of a surfactant {AZPEG1000} (trade name, manufactured by Dojindo Co., Ltd.) and 8.9 g of a carbon black black pigment were added. After stirring, 30 minutes with an ultrasonic homogenizer [150W, 20K HZ] while cooling with water.
Dispersion was performed for a minute to obtain a black dispersion.

(Preparation of Transparent Resin Liquid) 20 parts by weight of methacrylic acid, 15 parts by weight of hydroxyethyl methacrylate, 10 parts by weight of methyl methacrylate and 55 parts by weight of butyl methacrylate were dissolved in 300 parts by weight of ethyl cellosolve.
Under a nitrogen atmosphere, 0.75 parts by weight of azobisnitrile was added, and the resulting acrylic resin was reacted at 70 ° C. for 5 hours. The resulting acrylic resin was diluted with ethyl cellosolve to a resin concentration of 10% by weight to obtain a transparent resin liquid. Was.

(Formation of Color Pixel Pattern) As the substrate (15), low expansion glass manufactured by Corning Co., Ltd. [Product No. 70]
59] and a thickness of 1.1 mm. As shown in FIG. 2A, Al was sputtered on the substrate (15).
A thin film electrode (14) functioning as a cathode was formed to a thickness of about 5 μm. This corresponds to the electrode (1) in FIG. Next, 1.2 μm of a positive photoresist (AZ1350, manufactured by Hoechst) was applied and dried at 100 ° C. for 20 minutes to form a photoresist layer (3).

Next, as shown in FIG. 1 (b), a 12 mJ / cm ² UV exposure is performed through a positive type mask and developed with a designated developing solution, and as shown in FIG. 1 (c) and FIG. Then, only the photoresist layer (3) in the portion where the red pixel (5R) was to be formed was removed, and the electrode was exposed to form a pattern electrode (4).

The pattern electrode (4) is connected to a metal electrode (30) acting as an anode, as shown in FIG.
Immersion in the red dispersion at room temperature for about 15 minutes
As shown in (d) and FIG. 5, a pattern electrode having a red pixel (5R) formed on the exposed electrode was obtained. After washing with distilled water, drying was performed in an oven at about 70 ° C. for about 20 minutes.

Next, the transparent resin was applied, and 5 × 10 ³
After reducing the pressure at 10 × 10 ³ Pa for about 10 seconds, the excess transparent resin was shaken off with a spinner and dried at 70 ° C. for 30 minutes. Next, the pattern electrode was heated to about 70 ° C. for about 3 hours.
Heat treatment was performed for 0 minutes to obtain a pattern electrode on which a red pixel (6R) impregnated with a transparent resin was formed as shown in FIG.

Subsequently, the same operation as that for forming the red pixel (6R) was repeated using the green dispersion liquid and the transparent resin liquid to obtain a green pixel (6G). Subsequently, the same operation is repeated using the blue dispersion liquid and the transparent resin liquid,
A blue pixel (6B) was obtained. Thereby, as shown in FIG. 1F and FIG. 6, the red pixel (6R) and the green pixel (6R)
G) A pattern electrode on which blue pixels (6B) were formed was obtained.

Next, 1 through a positive mask for a light shielding film.
After performing ² mJ / cm ² UV exposure and developing with a designated developing solution, as shown in FIG. 1 (g), the photoresist layer (3) between the pixels of each color and around the pixel area is removed, and the pattern electrode is formed. (4) A photoresist layer remaining portion (13) is formed on the edge at a width of about 10 mm, and the same operation as the formation of the red pixel (6R) is repeated using the black dispersion liquid and the transparent resin liquid. (H) and a black light-shielding portion (7) shown in FIG. 7 were obtained. Subsequently, the remaining photoresist layer at the edge of the substrate (13)
Was removed using 5% caustic soda.

(Transfer) As the adhesive (11), a heat-sensitive adhesive (No. 28-18-, manufactured by Toyo Ink Mfg. Co., Ltd.)
3) was replaced with a 1.1 mm thick low expansion glass (Corning, 7
059), and dried at 40 ° C. to form a substrate (2). Adhesive thickness is about 15μ
m. Next, the substrate (2) coated with the adhesive (11)
Is heated to 100 ° C. to cause the adhesive to exhibit adhesiveness, and then, as shown in FIG. (7)
The pixel surface of the electrode (1) on which was formed was adhered to the adhesive surface by applying a pressure of 5 kg / cm ^{2 with} a laminator. After confirming the state of adhesion, only the electrode (1) was peeled off to complete the transfer.

Next, the adhesive, the pixel, and the light-shielding portion are cured by post-baking at 230 ° C. for 60 minutes.
A transmission type color filter was obtained. The film thickness of the pixel excluding the adhesive was about 1.0 μm.

(Formation of Protective Film) Subsequently, a red pixel (6R), a green pixel (6G), and a blue pixel were used as the material of the protective film using the product name "Optomer SS7265" manufactured by Nippon Synthetic Rubber Co., Ltd. (6B) and a black light-shielding portion (7) are formed into a film, and the remaining photoresist layer (13) at the edge of the substrate is uniformly applied on a substrate from which the photoresist layer has been removed. The film was cured by heating for about 1 hour to form a protective film (8). As described above, a color filter (10) as shown in FIG.

When the surfaces of the red pixel (6R), green pixel (6G), and blue pixel (6B) of the obtained color filter (10) were observed with a scanning electron microscope, the maximum particle diameter was about 0.1 μm. The following fine particles were confirmed. The spectral transmittance of each of the red pixel (6R), green pixel (6G), and blue pixel (6B) of the obtained color filter (10) was measured. It was confirmed that the spectral transmittance of each pixel was improved by about 7% to 13%. Further, when a liquid crystal display device was prepared using the obtained color filter (10), the film strength and adhesion strength of the color filter were sufficient. Further, the hardness of the pixels of the obtained color filter (10) was measured by a measuring method according to a pencil scratch value test of JIS (K5400-1990).
H or more.

<Example 2> In Example 1, only the substrate used for the transfer was a 1.1 mm-thick low-expansion glass (Corning, 7059), and a light-reflective substrate mirror-finished by electrolytic polishing was used. It was used. That is, except for the substrate used for transfer, each dispersion liquid, transparent resin liquid,
Materials such as an adhesive and a protective film, and methods and conditions for forming a color pixel pattern, applying an adhesive, transferring, post-baking, and forming a protective film are the same as those in the first embodiment. When the light reflectance of the obtained color filter was measured, it was confirmed that the light reflectance was improved by about 5% to 7% as compared with the light reflectance of the color filter according to the conventional method using the same pigment.

<Comparative Example 1> In Comparative Example 1, a transparent thin film was formed on a transparent substrate, and the transfer as in the above embodiment was not performed using the transparent substrate on which the transparent thin film was formed. A color filter was produced. That is, in the manufacturing process, a protective film is formed after the process steps (a) to (li) in FIG. As the substrate (15), low expansion glass [product number 7059], manufactured by Corning Co., Ltd., having a thickness of 1.1 mm was used. On this substrate (15), FIG.
(B) As shown in FIG.
A transparent thin film (16) functioning as a cathode was formed. This corresponds to the electrode (1) in FIG. An Al plate having a thickness of about 1 mm was used as a metal electrode acting as an anode. Each dispersion, transparent resin liquid, material such as protective film, and
The methods and conditions for forming a color pixel pattern, post-baking, and forming a protective film are the same as those in the first embodiment. When the light transmittance of the obtained color filter was measured, the light transmittance was reduced by the transparent thin film (ITO) on the transparent substrate. It was confirmed that it decreased by ~ 20%.

<Comparative Example 2> In Comparative Example 2, a light-reflective substrate was used as a substrate, and a reflection type color filter was manufactured without performing transfer as in the above-described embodiment. That is, in the manufacturing process, a reflective color filter is manufactured in the steps (a) to (i) in FIG.
As the substrate (1), a light-reflective substrate obtained by subjecting an Al plate having a thickness of 1.5 mm to a mirror finish by electrolytic polishing is used. This corresponds to the electrode (1) in FIG. Materials such as each dispersion liquid, transparent resin liquid, and a method of forming a color pixel pattern, post-baking,
The conditions are the same as in Example 1. When the reflection transmittance of the obtained color filter was measured, partial ionization of the Al plate surface due to the reduction of the surfactant, scattering of light due to elution, and a decrease in reflectance occurred. It was confirmed that the reflectance was reduced by about 5% to 15% as compared with the reflection transmittance.

In the present invention, micelles are formed by wrapping the coloring pigment with the surfactant on the hydrophobic part inside and the hydrophilic part on the outside to form micelles. It is finely divided into a state. Then, only by the destruction of the micelles, the color pigment which is finely divided into the primary particles or a state close to the primary particles is formed on the electrode, so that the liquid crystal display having good color characteristics in which the color characteristics possessed by the color pigment are not reduced An apparatus color filter is obtained. Further, in the present invention, since the transparent resin is impregnated in the thin film of the color pigment, a color filter in which a decrease in film strength or adhesion strength is prevented can be obtained. Further, in the present invention, since a binder resin is not used as a material, dispersibility, anti-agglomeration, and other properties are not restricted, and a transparent resin material having excellent heat resistance and transparency can be selected and obtained. The color characteristics of the color filter are good with little reduction in the performance of the color characteristics of the color pigment. Further, in the present invention, after the electrode on which the color pigment pattern is formed is adhered to the transparent substrate via the transparent adhesive, only the electrode is peeled off, and only the color pigment pattern is transferred to the transparent substrate. A color filter for a liquid crystal display device which does not decrease the transmittance can be obtained. Further, in the present invention, after the electrode on which the color pigment pattern is formed is adhered to the light-reflective substrate via a transparent adhesive, only the electrode is peeled off, and only the color pigment pattern is applied to the light-reflective substrate. Because it transfers, there is no scattering of light due to partial ionization and elution of the light-reflective substrate, and no decrease in reflectance occurs.
A color filter for a reflection type liquid crystal display device which does not decrease the reflectance can be obtained.

[Brief description of the drawings]

FIGS. 1 (a) to 1 (e) are cross-sectional views showing one embodiment of a process for manufacturing a color filter according to the present invention.

FIGS. 2A and 2B are cross-sectional views showing another example of a substrate or a film serving as a temporary support.

FIGS. 3A and 3B are cross-sectional views illustrating examples of a reflection type color filter.

FIG. 4 is a plan view of a patterned electrode according to the present invention from which a photoresist layer is removed in a pattern.

FIG. 5 is a plan view of a pattern electrode on which a red pixel is formed.

FIG. 6 is a plan view of a pattern electrode in which a red pixel, a green pixel, and a blue pixel are formed and impregnated with a transparent resin.

FIG. 7 is a plan view of a pattern electrode in which a red pixel, a green pixel, a blue pixel, and a black light-shielding portion are formed and impregnated with a transparent resin.

FIG. 8 is an explanatory diagram showing a state in which a pattern electrode and a metal electrode are immersed in a processing solution.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Electrode 2 ... Transparent substrate 3 ... Photoresist layer 4 ... Pattern electrode 5R ... Red pixel 5G ... Green pixel 5B ... Blue pixel 6R ... Red pixel impregnated with transparent resin 6G ... Green pixel impregnated with transparent resin 6B ... Transparent resin 7 ... Black light shielding part 8 ... Protective film 9 ... UV light irradiation 10 ... Color filter 11 ... Adhesive 12 ... Light reflective substrate 13 ... Remaining photoresist layer 14 ... Thin film 15 ... Substrate or film 16 ... Transparent Thin film 20 ... Positive mask 22 ... Substrate 30 ... Metal electrode 32 ... Light reflective thin film 40 ... Treatment liquid 50 ... Connection part 70 ... Reflection type color filter

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Makoto Sakakawa 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd.

Claims (5)

[Claims] (1) a step of providing a photoresist layer on a metal or metal oxide electrode which is more base than a surfactant; (2) exposing and developing a pattern of a predetermined color to the photoresist layer; (3) a step of patterning and exposing the electrode in a pattern; and (3) disposing the electrode in a treatment liquid in which a surfactant that can be electrolytically reduced on the electrode surface and an organic or inorganic color pigment are dissolved or dispersed as fine particles. By immersing the lower electrode and the electrode in an electrically connected state, a surfactant in the vicinity of the exposed electrode is subjected to electrolytic reduction, and the coloring pigment is attached to the exposed electrode. (4) a step of applying a transparent resin on the colored pigment adhered to the exposed electrode and drying it, and impregnating the colored pigment with the transparent resin; and (5) performing the above steps (2) to (4) for each color. To (6) removing the remaining photoresist layer through the steps (1) to (5), and applying the electrode to which the color pigment pattern obtained in the steps (1) to (5) is adhered to the electrode via a transparent adhesive. A method of manufacturing a color filter for a liquid crystal display device, comprising: a step of, after adhering to a transparent substrate with a color pigment inside, removing only the electrode and transferring only a pattern of the color pigment to the transparent substrate. 2. The method for producing a color filter for a liquid crystal display device according to claim 1, wherein said surfactant contains an aromatic azo compound residue in a hydrophobic portion thereof. 3. The method for producing a color filter for a liquid crystal display device according to claim 1, wherein said solvent is water or a mixed solvent of water and an organic solvent compatible with water. 4. The method for producing a color filter for a liquid crystal display device according to claim 1, wherein the color pigment is hydrophobic or weakly hydrophilic. 5. The method according to claim 1, wherein the transparent substrate is a light-reflective metal or metal oxide substrate, or a substrate provided with a light-reflective metal or metal oxide thin film. Of manufacturing a color filter for a liquid crystal display device.