JP2003287614A - Method for manufacturing color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a color filter with spacers attached thereon being in no danger of conduction to a counter substrate and easy-touse at a low cost, with high accuracy and with low defective fraction, which is difficult to be realized with a conventional method for manufacturing a color filter. <P>SOLUTION: In the method for manufacturing the color filter having a resin film pattern on a substrate, the method for manufacturing the color filter is characterized by having a step to apply a resin solution on the substrate and form the resin film (1), a step to make a laser beam irradiate the desired region of the resin film with a laser beam irradiating device (2) and a step to remove a part of the resin film, which is not irradiated by the beam, with a developer (3). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a color filter having a resin film pattern on a substrate.

[0002]

2. Description of the Related Art Generally, color filters are made of glass,
It has a resin film pattern on a substrate such as a polymer film. Examples of the resin film pattern include a black matrix made of a resin containing a light shielding material, a pixel made of a resin containing a colorant, an overcoat, and a spacer.

As a method of forming a resin film pattern, there is a photolithography method. The photolithography method is roughly divided into two. One is a method of applying, exposing, and developing using a photosensitive resin containing a photopolymerization initiator. the other one is,
Apply the photosensitive resin film on the non-photosensitive resin film, and then
This is a method of performing exposure, development, and, if necessary, etching. These photolithography methods have many steps and have a problem of yield reduction. Moreover, since a photomask is usually used during exposure, the cost of the photomask becomes a problem. In particular, as the substrate size increases, it is necessary to create a large photomask with high accuracy, and the cost of the photomask becomes very high.

Other methods for forming a resin film pattern include a printing method, an ink jet method and a laser ablation method.

The printing method does not require a photomask,
There is a problem of printing alignment and bleeding, and it is not possible to form a high precision pattern.

The ink jet method also does not require a photomask, but too many dots need to be processed to form a pattern, which is problematic in terms of accuracy, tact, and yield.

The laser ablation method is a method in which a resin film is irradiated with laser light to evaporate the resin film in the irradiation region to form a pattern. In the laser ablation method, when a resin film is evaporated by laser light, a modified product of the resin film may remain in the surroundings, or burrs may be formed on the evaporated edge. It is easy to cause defects.

On the other hand, in the conventional liquid crystal display device, in order to maintain the thickness (cell gap) of the liquid crystal layer,
Generally, plastic beads, glass beads, glass fibers, etc. are sandwiched between two substrates for liquid crystal display devices to be used as spacers. Since spacers such as plastic beads are sprayed on the airflow, it is difficult to control the spraying position of the spacers, and there are spacers in the display area of the liquid crystal display device (the light transmissive part in the screen except the light shielding part). . There is a problem that the display quality of the liquid crystal display device is deteriorated by the light scattering by the spacer.

Further, when a spacer such as plastic beads is placed on an air stream and is sprayed, the spacer may not be uniformly sprayed due to the influence of the air stream or static electricity, and the spacer may be aggregated. When the spacers aggregate, the display quality of the aggregated portion deteriorates, and there is a problem in that the cell gap is accurately retained.

To solve this problem, a color filter with a spacer has been proposed which uses a protrusion formed on the color filter as a spacer. As a method of forming the protrusion, there are a method of laminating colored layers of two colors or three colors, and a method of forming the protrusion by a separate protrusion forming step after forming the color filter. The former method is advantageous in terms of cost because the spacer can be formed at the same time as the pixel of the color filter is formed, so that the number of steps for forming the spacer is not increased, but the transparent conductive film which is a liquid crystal driving electrode is formed on the spacer. There is a drawback that a film is formed. When such a spacer abuts against the counter substrate and secures the cell gap, consideration must be given to disposing an insulating layer on the counter substrate in order to avoid a short circuit between the transparent conductive layer on the spacer and the counter substrate. Becomes

On the other hand, in the latter method, since the spacer is formed after the color filter is formed, the number of steps is increased and there is a cost problem.

Therefore, in order to manufacture a color filter with a spacer which is easy to use at a low cost, a resin film pattern forming technique with a low cost, a short tact, a high accuracy, and a low defective rate is required.

[0013]

As described above, it has been difficult to obtain a resin film pattern having a low cost, a short tact, a high accuracy, and a low defect rate by the conventional method.

The present invention overcomes the drawbacks of the prior art,
An object of the present invention is to provide a method for forming a resin film pattern that satisfies low cost, short tact, high accuracy, and a low defective rate, and particularly to provide a spacer forming method for a color filter with a spacer.

[0015]

As a result of various studies conducted by the present inventors in order to solve the above-mentioned problems, they arrived at the color filter manufacturing method of the present invention.

That is, the object of the present invention is achieved by the following color filter manufacturing method. (1) In a method of manufacturing a color filter having a resin film pattern on a substrate, (1) a step of applying a resin solution on the substrate to form a resin film, and (2) a desired resin film by a laser irradiation device. A method for producing a color filter, comprising: irradiating a region with a laser beam; and (3) removing a non-irradiated portion of the resin film with a developing solution. (2) In the step of irradiating the desired region of the resin film with the laser beam by the laser beam irradiating device, the method of irradiating the desired region with the laser beam is either a method of moving the laser beam or a method of moving the substrate. One or a combination of both, the method for producing a color filter according to (1). (3) The laser light irradiation device uses the third harmonic of a YAG laser as a light source (1) or (2)
The method for manufacturing a color filter according to. (4) The method for producing a color filter according to any one of (1) to (3), wherein the laser light irradiation device has a polygon mirror in the optical system. (5) The laser light irradiation device has at least an optical system including a laser light source, a collimator lens, a polygon mirror, and an fθ lens (1)
~ The method for producing a color filter according to any one of (4). (6) The method for producing a color filter according to any one of (1) to (5), wherein the resin film is an acrylic photosensitive resin resin film. (7) The method for producing a color filter according to any one of (1) to (6), wherein the resin film pattern is a spacer formed on the color filter.

[0017]

The substrate used in the color filter of the present invention is not particularly limited,
Quartz glass, borosilicate glass, aluminosilicate glass, inorganic glass such as silica-coated soda lime glass, plastic film, or sheet is used. An opaque substrate such as a metal plate can also be used as the color filter of the reflective liquid crystal display device.

A black matrix is provided on this substrate as needed. The black matrix is a light-shielding region between pixels and plays a role of improving the contrast of the liquid crystal display device, but it may be formed by a metal thin film having a fine pattern or a lamination of these metals with a partial oxide film. Many. Cr, Ni, Al or the like is used as the metal. As a method of forming a metal thin film, a sputtering method, a vacuum deposition method, or the like is widely used. For fine patterns, after forming a photoresist pattern on the metal thin film by photolithography,
It is obtained by etching the metal thin film using this resist pattern as an etching mask.

However, since the black matrix formed of a metal thin film or the like uses the vacuum thin film forming method, the manufacturing cost is high, which causes the price increase of the color filter. Further, Cr, which is generally used as a metal thin film for a black matrix, is a heavy metal and is not preferable from the environmental point of view.

Therefore, as the black matrix,
It is preferable to use a resin black matrix in which a light shielding agent is dispersed in a resin.

Examples of the light-shielding agent used for the resin black matrix include carbon black, metal oxide powders such as titanium oxide, titanium oxynitride, and iron tetraoxide, metal oxynitrides, metal sulfide powders, and metal powders. Besides, a mixture of red, blue, and green pigments can be used. Among these, carbon black is particularly preferable because it has excellent light-shielding properties.

When carbon black is used as the light-shielding agent, it is preferable to mix a pigment having a complementary color of carbon black in order to make the color tone achromatic. As the complementary color pigment, a blue pigment and a purple pigment may be used alone or in combination of both.

When carbon black and a pigment having a complementary color to carbon black are used as the light-shielding agent, the proportion of carbon black contained in the light-shielding agent should be 50% by weight or more in order to obtain a high light-shielding property. Is preferable, more preferably 60% by weight or more, and further preferably 70% by weight or more.

On the other hand, as the resin used for the resin black matrix, epoxy resin, acrylic resin, polyimide resin, urethane resin, polyester resin are considered from the viewpoint of heat resistance, light resistance and solvent resistance of the coating film. It is preferable to use a polyolefin resin.

The resin black matrix is formed by applying a black paste for resin black matrix onto a substrate, drying and then patterning. As a method for applying the black paste, a dip method, a roll coater method, a spinner method, a die coating method, a wire bar coating method or the like is preferably used, and thereafter, using a vacuum dryer, an oven, a hot plate, or the like, Drying and heating (semi-cure) are performed. The semi-cure conditions vary depending on the resin and solvent used, but are usually 40 to 200 ° C.
It is common to heat for 1 to 60 minutes.

The black paste coating film thus obtained is used as it is after the photoresist film is formed on it when the resin is non-photosensitive and when the resin is photosensitive. Alternatively, patterning is performed by exposing and developing after forming the oxygen blocking film. Then, if necessary, the photoresist film or the oxygen blocking film is removed, and then the film is heated and dried (main curing). The curing conditions will differ depending on the type of resin used, but it is common to heat at 150 to 300 ° C. for 1 to 60 minutes.

Besides this, the resin black matrix may be formed by a transfer method, a printing method, an electrodeposition method, an ink jet method or the like.

The thickness of the resin black matrix is preferably 0.5 to 2.0 μm, more preferably 0.8 to 1.
It is 5 μm. If the film thickness is less than 0.5 μm,
If the light shielding property is insufficient and the film thickness is thicker than 2.0 μm, the flatness of the color filter surface becomes poor.

The light-shielding property of the resin black matrix is OD
It is represented by a value (common logarithm of reciprocal of transmittance), but in order to improve the display quality of the liquid crystal display device, preferably 1.
It is 6 or more, and more preferably 2.0 or more. Further, the preferable range of the film thickness of the resin black matrix has been described above, but the upper limit of the OD value is determined in relation to this.

Between the resin black matrices, usually 2
An opening of 0 to 200 μm × 20 to 300 μm is provided, and a plurality of colored layers of the three primary colors are arranged so as to cover at least the opening. That is, one opening is covered with any one of the colored layers of the three primary colors, and a plurality of colored layers of each color are arranged.

Further, as the black matrix, a layer in which colored layers are stacked may be used. In this case, since the step of forming the black matrix can be omitted,
preferable.

On the color filter of the present invention, a colored layer composed of three primary colors is formed. As the colored layer, a layer in which a dye is dispersed in a resin can be used. Dyes can be used in combination as appropriate to represent the three primary colors. The pigments that can be used are red, orange, yellow, green,
Examples include, but are not limited to, blue and purple pigments and dyes. As the resin, it is preferable to use epoxy resin, acrylic resin, polyimide resin, urethane resin, polyester resin, or polyolefin resin in view of heat resistance, light resistance, and solvent resistance of the coating film. .

As a method for forming the colored layer, the same method as for the resin black matrix can be adopted. After the pattern of the colored layer of the first color is formed on the substrate, the same operation is repeated to form the colored patterns of the second and third colors.

In the color filter of the present invention, a transparent protective film can be formed after forming the colored layer. The formation of the transparent protective film is advantageous from the viewpoint of preventing impurities from seeping out from the color filter and flattening the surface of the color filter.

As the transparent protective film, an acrylic resin, an epoxy-modified acrylic resin, an epoxy resin, a siloxane polymer, a silicone polyimide, a benzocyclobutene resin or the like can be used, but from the viewpoint of excellent flattening characteristics, an epoxy resin is used. It is preferable to use a modified acrylic resin or an epoxy resin, and it is preferable to use a siloxane polymer or a silicone polyimide from the viewpoint of excellent blocking of impurity components.
Further, in order to achieve both the flattening property and the impurity blocking property, it is preferable to use an epoxy-modified acrylic resin having a siloxane bond, an epoxy resin having a siloxane bond, or a benzocyclobutene resin having a siloxane bond.

The thickness of the transparent protective film is 0.02 μm to 3 μm.
It is preferably m. When the thickness is less than 0.02 μm, not only is the blocking property of the impurity component insufficient, but also the planarization is insufficient. When the transparent protective film is thicker than 3 μm, it is preferable in terms of blocking impurity components, but it is not preferable because particles produced by drying the transparent protective film reduce the production yield. The thickness of the transparent protective film is more preferably in the range of 0.03 μm to 2 μm, and most preferably in the range of 0.04 μm to 1.5 μm.

In the color filter of the present invention, 3
If necessary, a transparent conductive film can be formed after forming the primary color layer or after forming the transparent protective film. As the transparent conductive film, an oxide thin film such as ITO is adopted,
Usually, an ITO film having a thickness of about 0.1 μm is formed by a sputtering method or a vacuum evaporation method.

In the color filter of the present invention, a spacer can be formed on the colored layer, the transparent protective film or the transparent conductive film. The part to be formed may be any of the above according to the structure of the color filter.

The shape of the spacer, that is, the shape of the cross section when the spacer is cut along a plane parallel to the substrate is not particularly limited, but is a circle, an ellipse, a polygon with rounded corners, a cross, a T-shape, or an L-shape. Glyphs are preferred. Further, it is preferable that the area of the contact portion of the spacer with the counter substrate is designed to be smaller than the area of the spacer bottom portion.

The height of the spacer is preferably 1 to 9 μm. If the height of the spacer is less than 1 μm, a sufficient cell gap cannot be secured. On the other hand, if it exceeds 9 μm, the cell gap of the liquid crystal display device becomes too large and the voltage required for driving becomes high, which is not preferable. Note that the spacer height means the distance between the surface of the black matrix opening of the color filter and the uppermost surface of the spacer, focusing on one spacer. When the height of the flat portion of the display portion on the substrate is uneven, it means the maximum distance between the uppermost surface of the spacer and the flat portion surface of each black matrix opening position.

From the viewpoint of improving the uniformity of the space between the two liquid crystal display device substrates held by the spacer in the screen,
It is preferable to form the spacer in the non-display area inside the screen and outside the screen, but in some cases, the spacer may be formed in either the non-display area inside the screen or outside the screen.

The area and the location of each spacer are greatly influenced by the structure of the liquid crystal display device. Constraints of the area of the non-display region 1 in the pixel in a color filter having a fixed spacer, the spacer area per one of the screen is preferably 10μm ² ~1000μm ^2. More preferably, 10 μm ^{2 to} 25
It is 0 μm ² . The spacer area as referred to herein is the area of the top of the spacer formed on the color filter, and is the area of the portion that comes into contact with the counter substrate when the liquid crystal display device is manufactured, or is formed on the counter substrate. The area of the part that contacts the spacer. When the area of each spacer is smaller than 10 μm ^2, it becomes difficult to form a precise pattern and stack, and the spacer may be destroyed by the pressure applied during the production of the liquid crystal display device.
On the other hand, when the area of each spacer is larger than 1000 μm ^2, it becomes difficult to perform sufficient alignment treatment by rubbing around the spacer. Further, it is difficult to completely dispose the spacer in the screen in the non-display area in the screen, depending on the shape of the spacer portion. on the other hand,
Off-screen spacers never appear in the display area. Therefore, in the case of a liquid crystal display device having a spacer inside and outside the screen, the area per spacer outside the screen is equal to the area per spacer inside the screen in order to facilitate spacer formation. It is preferably equal to or greater than. The spacer can be provided outside the screen and also in a light-shielding portion called a frame that surrounds the screen. Although the spacer is formed on the color filter, it is also possible to form a spacer at the spacer abutting position on the color filter counter substrate and use the spacer on the color filter and the spacer on the counter substrate by abutting. is there.

The spacer material is not particularly limited as long as it is a photosensitive resin. As the photosensitive resin, there are types such as photodecomposition type resin, photocrosslinking type resin, and photopolymerization type resin, but in the present invention, a negative type photosensitive resin in which a light irradiation part is cured and becomes insoluble in a developing solution. Since it is preferable to use a photosensitive resin, it is preferable to use a photocrosslinking resin or a photopolymerization resin. In particular, a photosensitive composition containing a monomer, an oligomer or a polymer having an ethylenically unsaturated bond and an initiator that generates radicals by ultraviolet rays, a photosensitive polyamic acid composition and the like are preferably used. Specifically, it is preferable to use an acrylic photosensitive resin.

The acrylic photosensitive resin is composed of at least an acrylic resin, a photopolymerizable monomer and a photopolymerization initiator. Examples of the acrylic resin include acrylic acid, methacrylic acid, alkyl acrylates such as methyl acrylate and methyl methacrylate, alkyl methacrylates, or cyclic acrylates and methacrylates, or acrylates and methacrylates having a functional group such as hydroxyethyl acrylate and hydroxyethyl methacrylate. It is a resin obtained by copolymerizing a plurality of resins selected from the above. The acrylic resin may be a copolymer containing other monomers such as styrene, α-methylstyrene, acrylonitrile, itaconic acid ester, and fumaric acid ester. It is preferable to use one having a molecular weight of about 1,000 to 200,000. As the photopolymerizable monomer, bifunctional, trifunctional,
Polyfunctional monomers can be used. Examples of the bifunctional monomer include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, and triethylene glycol diacrylate, and examples of the trifunctional monomer include trimethylolpropane triacrylate and pentaerythritol triacrylate. Acrylate and the like, and polyfunctional monomers include ditrimethylolpropane tetraacrylate, dipentaerythritol penta, and hexaacrylate. Further, as the photopolymerization initiator, benzophenone, thioxanthone, imidazole, triazine compounds can be used alone or in a mixture, in the color filter manufacturing method of the present invention, in order to achieve a short tact, sensitivity of It is preferable to use a high photopolymerization initiator, and it is preferable to use an α-aminoalkylphenone photopolymerization initiator.

Further, an epoxy compound and an epoxy curing agent may be added to the photosensitive resin used in the present invention. Further, the acrylic resin may contain an epoxy group. Addition of these improves the strength as a spacer material. As the epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolac epoxy compound, a cresol novolac epoxy compound, a trishydroxyphenylmethane type epoxy compound, an alicyclic epoxy compound, a glycidyl ester type epoxy compound, a glycidyl amine type Epoxy compounds, heterocyclic epoxy compounds, fluorene group-containing epoxy compounds and the like can be used. On the other hand, as the curing agent, usual ones such as alcohol, phenol, amine, acid anhydride, carboxylic acid, and compound having active hydrogen can be used. Further, a cationic curing catalyst such as an onium salt may be used.

Further, the photosensitive resin used in the present invention may be added with a plasticizer, a filler or the like in order to improve the characteristics as a spacer.

As an example of the plasticizer, tributyl phosphate,
Phosphates such as triphenyl phosphate, phthalates such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, trimellitates such as trimethyl trimellitate and triethyl trimellitate, butyl oleate, etc. Of aliphatic monobasic acid ester, aliphatic dibasic acid ester such as dibutyl adipate, dihydric alcohol ester such as diethylene glycol dibenzoate,
Examples thereof include oxy acid esters such as acetyl tributyl citrate. Among them, preferable examples of the plasticizer include dioctyl phthalate and triethyl trimellitate.

The filler refers to a resin constituting the spacer, its solvent, and inorganic and organic particles having a property of being insoluble in a developing solution. As the inorganic particles, silica, barium sulfate, barium carbonate, calcium carbonate, extender pigments such as talc, and white, black, red,
Colored pigments such as blue and green, ceramic powders such as alumina, zirconia, magnesia, beryllia, mullite and cordierite, and glass-ceramic composite powders are used. Of the extender pigments, barite, barium sulfate, barium carbonate, calcium carbonate, silica and talc are not colored, and are preferably used when the spacer is desired to be transparent. When the spacer is required to have a light-shielding property, carbon black or titanium black (TiNxOy: where 0 ≦ x <1.5, 0.1 <y
<1.8), metal oxide powders such as manganese oxide and iron tetroxide, metal sulfide powders, and metal powders can be used. Among these, carbon black is particularly preferable because it has excellent light-shielding properties. When the spacer is required to have light-shielding properties and insulating properties, insulating inorganic particles such as aluminum oxide, titanium black, and iron oxide, or carbon black whose surface is coated with resin may be used. As the organic particles, organic pigments, beads of a polymer having a high molecular weight or a high degree of crosslinking, and the like are preferably used. The average particle size of the filler is preferably 5 to 40 nm, more preferably 6 to 35.
nm, and more preferably 8 to 30 nm. If the particle size of the filler is smaller than 5 nm, it is not sufficient to increase the strength of the spacer, and if it is larger than 40 nm, aggregation may be likely to occur. The filler is in the photosensitive resin,
In some cases, the particles may aggregate to form secondary particles, and when the average of the particle diameters is taken as the average secondary particle diameter, it is preferable to finely disperse so that the average secondary particle diameter becomes smaller. It is more preferable to disperse the primary particles with good stability. The average secondary particle diameter is preferably 5 to 100 nm, more preferably 6 to 88 nm, and further preferably 8 to 75 nm. If it is larger than this, unevenness is generated on the spacer surface, and disorder of liquid crystal alignment causes display defects, which is not preferable. The average primary particle diameter and the average secondary particle diameter are determined by, for example, observing the filler with a transmission electron microscope or a scanning electron microscope and determining the average particle diameter according to JIS-R6002. Further, the weight ratio of the filler to the resin in the spacer is preferably 3: 7 to 9: 1, and more preferably 4: 6 to 8: 2. When the weight ratio of the filler is too low, the strength of the spacer becomes low and the spacer is easily deformed. Further, if the weight ratio of the filler is too high, the filler may aggregate, which is not preferable. In the photosensitive resin of the present invention, as a method for dispersing the filler in the resin, there is a method in which the resin and the filler are mixed in a solvent and then dispersed in a disperser such as a triple roll, a side grinder or a ball mill. However, the method is not particularly limited. Further, various additives may be added in order to improve the dispersibility of the filler, or the coating properties and leveling properties.

The photosensitive resin of the present invention is preferably used in the form of being dissolved in a solvent. Examples of the solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethers such as diethylene glycol diethyl ether, ethyl acetate and n-butyl acetate. Three
-Methoxy-3-methylbutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetates, esters such as γ-butyrolactone, N, N-dimethylformamide,
Amides such as N, N-dimethylacetamide and pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone can be used.

The step of forming a spacer includes (1) a step of applying a resin solution for spacers on a substrate to form a resin film, (2) a step of irradiating a desired region of the resin film with light,
(3) A step of removing the non-irradiated portion of the resin film with a developing solution.

The coating method in the step (1) is not particularly limited, but a usual coating method such as a dip method, a roll coater method, a spinner method, a die coating method or a wire bar coating method can be used.

In the step (2) of irradiating the desired region of the resin film with light, an apparatus for irradiating the photosensitive resin with light can be used. As a method of irradiating light to a desired region, either one of a method of moving light and a method of moving a substrate, or a combination of both can be used. As a method of moving the light, a method of reflecting the light of the light source by a mirror driven by a galvano motor or a method of fixing the light source itself to an xy stage and moving it can be used. As a method of moving the substrate, a method of fixing the substrate on an xy stage and moving it can be used. In order to provide a spacer forming method satisfying low cost, short tact, high accuracy, and low defect rate, it is preferable to use a light irradiation device having a polygon mirror in the optical system. An optical system having a polygon mirror is generally a light source,
It is composed of a collimator lens, a polygon mirror, and an fθ lens. The light from the light source is collimated by the collimator lens and is condensed on the polygon mirror. The condensed light is reflected by the polygon mirror rotating at high speed and reaches the fθ lens. The fθ lens plays a role of correcting the light reflected by the polygon mirror and irradiating the light to a desired position. A light irradiation device having such an optical system can hit a dot of light at a desired position with high speed and high accuracy, and an isolated resin film pattern such as a spacer can be manufactured at low cost, short tact, high accuracy, and It is a device suitable for forming in a form that satisfies a low defect rate. The light source is not particularly limited as long as it irradiates light that sensitizes a photosensitive resin, but it is preferable to use a laser as a light source because it is easy to obtain parallel light and it is easy to control the irradiation amount. . As the laser, the third harmonic (355 nm) of a YAG (yttrium aluminum garnet crystal) laser or the like can be used. Here, the third harmonic of the YAG laser is
It can be obtained by converting YAG laser light with a nonlinear optical crystal. As the nonlinear optical crystal, for example, a rare earth / calcium / oxyborate-based crystal can be used. As for the irradiation amount of light, it is sufficient to irradiate the photosensitive resin so that the photosensitive resin is exposed to light and pattern processing is possible. Specifically, 10 mJ / cm ^{2 to} 300 mJ / cm ²
It is preferable to irradiate in the range. Irradiation dose is 10 mJ /
If it is smaller than cm ² , the photosensitivity of the photosensitive resin is not sufficient and pattern processing cannot be performed. Further, when the irradiation amount is larger than 300 mJ / cm ² , there is a problem that the irradiation takes time, the tact becomes long, and the throughput decreases. If irradiation of the desired spacer portion is not completely completed within the determined tact, a plurality of light irradiation devices may be used. In this case, a plurality of devices may be used, or an irradiation device having only a plurality of optical systems may be used.

The developing method in the step (3) is not particularly limited, but an immersion method, a spray method, a paddle method or the like can be used. After the development, a washing process using pure water or the like may be added as appropriate. Also, high pressure rinse or brush cleaning can be adopted. As the developing solution, water, an alkaline solution, an organic solvent, or a mixture thereof is used. As the alkaline solution, a solution in which an inorganic or organic alkaline compound is dissolved in water is generally used. A known surfactant may be appropriately added to the developer.

In the method of manufacturing a color filter of the present invention, exposure is performed by laser light without using a photomask. Since the laser light is excellent in straightness, the pattern obtained by exposure and development has a pattern top portion and a pattern bottom portion that have substantially the same shape. For example, if the laser light is circular, the obtained pattern will be cylindrical. On the other hand, in the exposure using a normal photomask, the light leaks to the side of the pattern due to the diffraction of the light by the mask, so that the obtained pattern has a different shape at the top and bottom of the pattern. For example, when the photomask has a circular shape, the obtained pattern has a truncated cone shape. It is important to form both the top and bottom of the spacer in the non-display area. In the future, as the aperture ratio increases, the non-display area where the spacer can be placed becomes narrower. The method for producing a color filter of the present invention, which can be formed into the above shape, is more preferable.

The method for producing the color filter of the present invention will be described below with reference to FIG. 1, but the present invention is not limited to this.

The black matrix 2 is formed on the non-alkali glass 1 using a black paste. The blue coloring layer 3 is formed so as to fill the openings of the black matrix 2. Similarly, a red colored layer is formed in the opening 4 of the black matrix 2 and then a green colored layer is formed in the opening 5 of the black matrix 2. Next, the transparent protective film 6 is formed, and the transparent conductive film 7 is further laminated. After that, an acrylic photosensitive resin layer is formed on the transparent conductive film, and the spacer 8 is formed by laser exposure and development.

The method for producing a color filter of the present invention comprises:
It is also effective for a color filter on array in which a color filter is formed on an array substrate in which driving elements such as TFTs and signal wirings are arranged on the substrate.

The color filter manufactured by the method for manufacturing a color filter of the present invention can be used in a personal computer, a word processor, an engineering workstation,
It can be suitably used for liquid crystal display devices such as navigation systems and liquid crystal televisions.

[0059]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto.

Example 1 (Production of Resin Black Matrix) 3,3 ', 4,4'
144.1 g of -biphenyltetracarboxylic dianhydride was mixed with 1095 g of γ-butyrolactone and 209 g of N-methyl-2-pyrrolidone, and 95.1 g of 4,4'-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldiphenyl Add 6.2 g of siloxane and add 3 at 70 ° C.
After reacting for a time, 2.96 g of phthalic anhydride was added and further reacted at 70 ° C. for 1 hour to obtain a polyimide precursor (polyamic acid) solution 1.

A carbon black mill base having the following composition was mixed with a homogenizer at 3 rpm at 7,000 rpm.
A black paste was prepared by dispersing for 0 minutes and filtering the glass beads.

Carbon Black Mill Base Carbon Black (MA100, manufactured by Mitsubishi Chemical Corporation):
4.6 parts Polyimide precursor solution 1: 24.0 parts N-methyl-2-pyrrolidone: 61.4 parts Glass beads: 90.0 parts Alkali-free glass of 300 × 350 mm size (manufactured by Nippon Electric Glass Co., Ltd.) , OA-2) Apply the black paste on the substrate using a spinner, and heat in an oven at 135 ° C.
It was semi-cured for 20 minutes. Subsequently, a positive photoresist (“Microposit” SRC100 30cp manufactured by Shipley Co., Ltd.) was applied by a spinner and dried at 90 ° C. for 10 minutes. The photoresist film thickness was 1.5 μm. Exposure was performed through a photomask using an exposure machine PLA-501F manufactured by Canon Inc.

Next, an aqueous solution containing 2% by weight of tetramethylammonium hydroxide at 23 ° C. was used as a developer.
The substrate was dipped in a developing solution, and at the same time, the substrate was oscillated so as to reciprocate once in a width of 10 cm for 5 seconds to develop a positive photoresist and etch the polyimide precursor at the same time. The developing time was 60 seconds. After that, the positive photoresist was peeled off with methyl cellosolve acetate and further cured at 300 ° C. for 30 minutes. In this way, the film thickness is 0.90 μm and the opening is 280 μm in the vertical direction.
m, and a grid-like black matrix having a width of 80 μm was provided. The screen size is 9.4 inches and the number of pixels is 64.
It was 0 × 480, and patterns for two surfaces were formed in the substrate. The OD value of the black matrix was 3.0. (Formation of colored layer) PR17 for each of red, green and blue pigments
A dianthraquinone pigment represented by No. 7, a phthalocyanine green pigment represented by PG36, and a phthalocyanine blue pigment represented by PB15: 6 were prepared. The above pigments were mixed and dispersed in the polyimide precursor solution 1 used for the black matrix to obtain three kinds of colored pastes of red, green and blue. A blue paste was applied on a resin black matrix substrate and semi-cured at 120 ° C. for 20 minutes. After this, a positive type photoresist (made by Shipley "Mi
90 ℃ after applying croposit "SRC100 30cp) with a spinner
And dried for 10 minutes. Exposure using a photomask, dipping the substrate in a 2% by weight aqueous solution of tetramethylammonium hydroxide, and simultaneously swinging the substrate so that it makes one reciprocation of a width of 10 cm for 5 seconds. The body was etched at the same time. Then, the positive photoresist was peeled off with methyl cellosolve acetate, and stripe-shaped blue colored layers having a width of about 90 μm and a length of 300 μm were formed in the width direction. further,
It was cured at 300 ° C. for 30 minutes. The thickness of the blue colored layer is 1.
It was 2 μm.

After the substrate was washed with water, stripe-like green and red colored layers were formed in the same manner as the blue colored layer, and the pixel intervals of the three colors were 10.
It was formed to have a thickness of μm. (Formation of transparent protective layer) Next, a transparent protective layer was laminated. The composition for transparent protective layer was synthesized by the following procedure. Acetic acid was added to methyltrimethoxysilane and hydrolyzed to obtain an organosilane condensate. 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride and 3-aminopropyltriethoxysilane were mixed in a N-methyl-2-pyrrolidone solvent at a molar ratio of 1: 2. , To obtain a condensate having an imide group. The composition for a transparent protective layer was obtained by mixing the organosilane mixture, the condensate having the imide group and N-methyl-2-pyrrolidone in a weight ratio of 5: 2: 4. This composition was applied onto a substrate on which a black matrix and colored layers for the three primary colors were formed and cured to obtain a transparent protective layer made of a polyimide-modified silicone polymer and having a thickness of 1.0 μm. (Formation of transparent conductive film) An ITO film having a film thickness of 150 nm and a surface resistance of 20 Ω / □ was formed on the substrate on which the transparent protective layer was formed by a sputtering method. (Formation of spacer) Methacrylic acid 30 g, methyl methacrylate 30
g, 40 g of styrene, and 2 g of N, N-azobisisobutyronitrile were mixed with 100 g of propylene glycol monomethyl ether acetate, reacted at 80 ° C. for 4 hours, cooled to room temperature, and 1 g of hydroquinone monomethyl ether was added. Glycidyl methacrylate (30 g) and triethylbenzylammonium chloride (3 g) were added to the obtained polymer and reacted at 75 ° C. for 3 hours to give an acrylic resin solution A having a double bond in the side chain.
Got A photosensitive resin solution having the following composition was applied using a spinner and dried at 90 ° C. for 10 minutes. The film thickness of the obtained photosensitive resin was 5 μm.

[0065]   Acrylic resin solution A 50 parts by weight   Dipentaerythritol hexaacrylate 20 parts by weight   Irgacure 369 (α-aminoalkylphenone photopolymerization initiator, Ciba Su     Made by Pecharty Chemical) 2 parts by weight   Ethyl cellosolve acetate 100 parts by weight Then the third harmonic of the Q-switched Nd-YAG laser
(355nm) as a light source, light source, collimator lens
, A polygon mirror, and an fθ lens
Exposure was performed by a light irradiation device having a. The exposure amount is
100 mJ / cm ²And One spacer for each pixel
Because of the formation, the total number of spacers in the substrate is 640 ×
480 x 2 = 614400, but the exposure time is 1
It was within minutes. Then, with a 1% aqueous solution of sodium carbonate
After development and washing with water, post bake at 220 ° C for 30 minutes
Perform and cure the resin to obtain the spacer
It was Spacer size is 10μ for both top and bottom
It has the same shape of m × 15μm, and there is no abnormality in the shape.
It was

Comparative Example 1 In the same manner as in Example 1, a black matrix, a coloring layer,
A transparent protective film and an ITO layer were formed. A photosensitive resin film was formed on the ITO layer in the same manner as in Example 1. After that, an exposure machine PLA-50 manufactured by Canon Inc. is used through a photomask provided with a light-shielding portion having a predetermined shape at the position where the spacer is formed.
Alignment exposure was performed using 1F. Then, in the same manner as in Example 1, development, washing with water and post-baking are performed,
A spacer was obtained.

The obtained spacer was the same as that used in Example 1, but a photomask was required, and the manufacturing cost was high.

[0068]

According to the method of manufacturing a color filter of the present invention, it is possible to provide a technique for forming a spacer of a color filter with a spacer at low cost, high accuracy, and low defect rate.

[Brief description of drawings]

FIG. 1 is an example of a cross-sectional view of a color filter manufactured by a method for manufacturing a color filter of the present invention.

[Explanation of symbols]

1: Glass substrate 2: Black matrix 3: Blue colored layer 4: Red coloring layer 5: Green colored layer 6: transparent protective layer 7: Transparent conductive layer 8: Spacer

Continued front page    F term (reference) 2H048 BA02 BA11 BA45 BB02 BB08                       BB44                 2H088 FA02 HA12 MA17 MA20                 2H089 LA09 LA16 MA04X MA05X                       NA05 NA14 NA17 QA12 TA12                       TA13                 2H091 FA02Y FA35Y FB04 FB12                       FB13 FC10 FD06 GA08 LA12

Claims (7)

[Claims] 1. A method of manufacturing a color filter having a resin film pattern on a substrate, the method comprising: (1) applying a resin solution onto the substrate to form a resin film; and (2) using the laser light irradiation device to form the resin film. 2. A method for producing a color filter, comprising: a step of irradiating a desired region with a laser beam; 2. In the step of irradiating a desired region of a resin film with a laser beam by a laser beam irradiation device, the method of irradiating the desired region with the laser beam is a method of moving the laser beam or a method of moving the substrate. The method for producing a color filter according to claim 1, wherein either one or a combination of both is used. 3. The method for manufacturing a color filter according to claim 1, wherein the laser light irradiation device uses a third harmonic of a YAG laser as a light source. 4. The method of manufacturing a color filter according to claim 1, wherein the laser light irradiation device has a polygon mirror in an optical system. 5. The laser light irradiation device comprises at least a laser light source, a collimator lens, a polygon mirror, and f.
The method for producing a color filter according to claim 1, further comprising an optical system including a θ lens. 6. The method for producing a color filter according to claim 1, wherein the resin film is an acrylic photosensitive resin resin film. 7. The resin film pattern is a spacer formed on a color filter.
7. The method for producing a color filter according to any one of to 6.