JP2003098333A - Method for manufacturing color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an excellent color filter leaving practically no residual film of a picture forming material after development on a picture non-forming part of a transparent substrate in the method for forming the color filter by transferring the picture forming material. SOLUTION: The method for manufacturing the color filter includes the steps of (1) tightly sticking a coloring photosensitive resin layer of the picture forming material disposed on a temporary supporting body to a transparent substrate under heating, (2) releasing the temporary supporting body, (3) pattern- exposing the photosensitive resin layer, (4) developing the photosensitive resin layer, (5) brushing the surface of the transparent substrate having the patterned and developed photosensitive resin layer in a liquid for removing the residual film after development containing at least a surfactant and simultaneously spraying a similar removing liquid for the residual film after development thereon under high pressure and (6) repeating the steps (1) to (5) with respect to the picture forming materials colored with different hues, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color filter used for a liquid crystal color display or the like,
In particular, the present invention relates to an effective method for removing a residual film after development in the manufacturing process.

[0002]

2. Description of the Related Art A liquid crystal display color filter has a structure in which red, green, and blue dot images are arranged in a matrix on a transparent substrate such as glass, and the boundaries thereof are divided by a black matrix. As a method for producing such a color filter, conventionally, a transparent substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method,
3) JP-A-63-298304, JP-A-63-309
No. 916 or JP-A-1-152449, etc., a colored photosensitive resin liquid method (colored resist method) by repeating coating, exposure and development of a colored photosensitive resin liquid, 4) JP-A-61 -99103, JP-A-61-2
As described in JP-A-33704 or JP-A-61-279802, a method of sequentially transferring images formed on a temporary support onto a final or temporary support 5).
As described in JP-A No. 61-99102, a colored layer is formed by applying a pre-colored photosensitive resin liquid on a temporary support, and the photosensitive layer is sequentially formed directly on the transparent substrate. There is known a method of forming a multicolor image by repeating a process of transferring a layer, exposing and developing the layer for the number of colors. In addition, a method such as an electrodeposition method or a vapor deposition method is known.

Then, a protective film for the purpose of physical and chemical protection of the color filter and flattening of the surface may be formed thereon. As the protective film, a highly transparent film such as an acrylic, urethane, or silicone resin film or a metal oxide film such as silicon oxide is applied by spin coating, roll coating, printing, etc., and if necessary. Generally, a method in which the film is left horizontal, the solvent is removed, and the resin is cured is generally used. Further, a transparent conductive film such as indium tin oxide (ITO) or tin oxide is formed thereon by a vacuum film forming method such as a sputtering method or a vacuum evaporation method, and then an electrode is formed by an etching method or the like. Patterning is performed to form a transparent electrode layer. The transparent electrode layer may be formed on the transparent substrate below the colored image and black matrix layer.

In the conventional main method of forming a colored image relating to the production of a color filter, 1) in the dyeing method, since the photoresist coating and the partial dyeing of the dried transparent film are repeated, the formation and removal of the dye-proof layer are repeated. It was necessary and the manufacturing process was complicated. 2) In the printing method, the transferability of the printing ink to the glass is inferior, so shape defects of the colored pattern and density unevenness are likely to occur, and it is also disadvantageous in the alignment of the patterns of three or four colors. It was difficult to produce a high-quality filter by In the method of 3), the density of the colored layer is determined by the thickness of the colored layer, and therefore an extremely precise coating technique was required to keep the density of the colored layer constant. Further, it is difficult to apply the second color layer after forming the first color because of the unevenness of the surface due to the first color layer, and it is actually difficult to obtain a uniform coating layer. Further, in the method of 4), it was difficult to properly arrange the images of the respective colors at desired positions (hereinafter, sometimes referred to as “registration”) at the time of transferring the colored images to the final support.
The method 5) is essentially excellent in that the steps of forming a colored image are simplified, exposure, development, and density control are easy, and in addition, no misalignment occurs in the transfer operation regarding the alignment of each colored image. . Further, since the colored photosensitive resin layer, which has been uniformly applied in advance with a constant thickness, is transferred, the exposure and development characteristics are stable, and the optical density of the final colored image obtained can be easily controlled.

However, since the method of heat transfer is used, a part of the photosensitive resin layer is thermally polymerized by the heat at the time of transfer, and after the development treatment, it is not exposed at the non-image forming portion of the transparent substrate, that is, patterning and development. The thermal polymer tends to remain as a thin residual film in the portion where the photosensitive resin layer is removed in the process.
This residual film causes color mixing and also causes a decrease in adhesive strength when the two substrates are joined together by an adhesive in the non-image forming portion for assembling into the liquid crystal panel.

In order to avoid the problems caused by the residual film, for example, Japanese Patent Laid-Open No. 6-258514 proposes a method of rubbing with a brush in a developing residual film removing liquid containing a surfactant as a main component. And some effect has been obtained. However, in recent years, so-called COA (C
color filter on alley) is becoming popular. In this case, the transparent electrode on the pixel and the TF are used.
A contact hole is formed in the pixel for the purpose of conducting the T electrode, but the effect of brush rubbing is not sufficient due to the extremely small hole of around 20μ, and a residual film is deposited on the electrode surface at the bottom of the contact hole, and the conduction occurs. The problem of causing defects occurs. In addition, the brush rubbing method has a problem that when it becomes excessive, it may damage the pixels or the array wiring.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to manufacture a color filter by a transfer method by removing a development residual film substantially completely without damaging a pixel or an array wiring to obtain a colored photosensitive resin. It is an object of the present invention to provide a manufacturing method that does not inhibit the adhesion of layers. Another object of the present invention is to provide a method for manufacturing a color filter that does not cause conduction failure in COA.

[0008]

The objects of the present invention have been achieved by the following means. <1> In the step of producing a color filter by transferring a plurality of colored photosensitive resin layers onto a transparent substrate, (1) an image forming material having a colored photosensitive resin layer provided on a temporary support,
A step of bringing the photosensitive resin layer into close contact with the transparent substrate while heating, and (2) a step of peeling the temporary support.
(3) a step of pattern-exposing the photosensitive resin layer,
(4) a step of developing the photosensitive resin layer, and (5) brushing the surface of the transparent substrate having the patterned and developed photosensitive resin layer in a residual development film removing solution containing at least a surfactant. In addition, the method includes the step of injecting the same chemical liquid at a high pressure and the step (6) of repeating the steps (1) to (5) for image forming materials colored in different hues. Color filter manufacturing method. <2> The method for producing a color filter according to <1> above, wherein the developer and the residual film removing solution do not substantially contain metal ions. <3> The development residual film removing liquid is an anionic surfactant,
And / or a nonionic surfactant, and an alkaline agent. The method for producing a color filter according to <1> above. <4> The method for producing a color filter according to <1>, wherein the transparent substrate is a TFT array substrate.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a color filter of the present invention comprises: (1) heating a photosensitive resin layer of the image forming material having a colored photosensitive resin layer provided on a temporary support on the transparent substrate. While closely contacting, (2) peeling the temporary support, (3) pattern exposing the photosensitive resin layer, (4) developing the photosensitive resin layer,
(5) a step of brushing the surface of the transparent substrate having the patterned and developed photosensitive resin layer in a residual development film removing solution containing at least a surfactant and spraying a similar chemical solution at high pressure; 6) Above (1) to (5)
Repeating each step for image forming materials colored in different hues. Hereinafter, the method for producing the image forming material, the colored photosensitive resin layer, the color filter, and the like will be described in detail.

(Image Forming Material) First, an image forming material in which a colored photosensitive resin layer is provided on a temporary support will be described. As a temporary support for the colored photosensitive resin layer used in the present invention, it is necessary that it has flexibility and does not undergo significant deformation, shrinkage or elongation even under pressure or under pressure and heating. Examples of such a support include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like. In particular, a biaxially stretched polyethylene terephthalate film is preferable because it has excellent mechanical and thermal properties.

On the temporary support, a colored photosensitive resin layer is provided directly or via an intermediate layer having an ultraviolet ray transmission property and a low oxygen transmission rate. Further, it is preferable to provide a thermoplastic resin layer (cushion layer) for the purpose of avoiding inclusion of bubbles during transfer. In this case, it is preferable that the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer are laminated in this order on the temporary support. The intermediate layer is formed by adhering the colored photosensitive resin layer to the transparent substrate, peeling the temporary support, and performing pattern exposure, from the air that inhibits the photocuring reaction in the colored photosensitive resin layer. It is provided as a barrier layer for preventing the penetration of oxygen and for preventing the thermoplastic resin layer and the photosensitive resin layer from being mixed with each other when the three layers are laminated.
Therefore, it is preferable that the colored photosensitive resin layer cannot be mechanically peeled from the colored photosensitive resin layer and that the oxygen blocking performance is high.

The intermediate layer is formed by applying a polymer solution onto a temporary support directly or via a thermoplastic resin layer. As a suitable polymer, Japanese Patent Publication No. 46-3
No. 2714 and Japanese Patent Publication No. 56-40824, polyvinyl ether / maleic anhydride copolymers, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl. Alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various water-soluble salts of starch and the like, styrene / malein. Mention may be made of acid copolymers, maleate resins, and combinations of two or more thereof.

Particularly preferred is the combination of polyvinyl alcohol and polyvinyl pyridone. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinylpyrrolidone is 1% by mass of the solid content of the intermediate layer.
To 75% by mass is preferable, and more preferably 1% to 6% by mass.
It is 0% by mass, more preferably 10% by mass to 50% by mass. If the content is less than 1% by mass, sufficient adhesion with the photosensitive resin layer may not be obtained, and if it exceeds 75% by mass, the oxygen blocking ability may be lowered. The thickness of the intermediate layer may be very thin, preferably about 0.1 to 5 μm, particularly preferably 0.2 to 2 μm. If the thickness is less than 0.1 μm, the oxygen barrier performance may be insufficient, while if it exceeds 5 μm, it may take too much time during development or removal of the intermediate layer.

As the resin constituting the thermoplastic resin layer,
It is preferable that the softening point is substantially 80 ° C. or lower. Examples of the alkali-soluble thermoplastic resin having a softening point of 80 ° C. or lower include saponification products of ethylene / acrylic acid ester copolymers, saponification products of styrene / (meth) acrylic acid ester copolymers, vinyltoluene and (meth) Saponified acrylic ester copolymer, poly (meth) acrylic ester,
At least 1 from a saponified product of a (meth) acrylate copolymer such as butyl (meth) acrylate and vinyl acetate.
Is preferably selected. In addition, "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Federation, published by Industrial Research Board, 1968, 10)
Of the organic polymers having a softening point of about 80 ° C. or less (on the 25th of a month), those soluble in an alkaline aqueous solution can be used.

Even for an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the polymer substance are added to the organic polymer substance to obtain a substantial softening point. It is also possible to use the one whose temperature is lowered to 80 ° C. or lower. Further, in order to adjust the adhesive force between these organic polymer substances and the temporary support, various polymers, supercooling substances, adhesion improvers or interfaces are used within a range in which the substantial softening point does not exceed 80 ° C. It is possible to add activators, mold release agents and the like. Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate,
Examples thereof include diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl phosphate.

The thickness of the thermoplastic resin layer is preferably 6 μm or more in order to function as a cushion layer. The reason for this is that if the thickness of the thermoplastic resin layer is 5 μm or less, it may not be possible to completely absorb the irregularities of the substrate of 1 μm or more, and bubbles may easily occur between the substrate and the substrate during transfer. is there. The upper limit is 100 μm or less, preferably 50 μm from the viewpoint of developability and production suitability.
It is the following.

(Photosensitive Resin Layer) The photosensitive resin layer is preferably softened or tacky at a temperature of at least 150 ° C. or less, and therefore it is preferably thermoplastic. Most of the layers using the known photopolymerizable composition have the above-mentioned properties, but some of the known layers can be further modified by adding a thermoplastic binder or a compatible plasticizer.

As the main component of the photosensitive resin layer of the present invention, all known photosensitive resins can be used. Specific examples include a photosensitive resin layer composed of a negative type diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. Among them, the photopolymerizable resin is particularly preferable. The photopolymerizable resin contains a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements. As the photosensitive resin, one that can be developed with an alkaline aqueous solution,
Although developable with an organic solvent are known, developable with an alkaline aqueous solution is preferable from the viewpoint of preventing pollution and ensuring labor safety.

Red, green, blue and black pigments which are the constituent colors of the color filter are further added to the photosensitive resin layer, and preferred examples of these pigments are Carmine 6
B (C.I. 12490), phthalocyanine green (C.I. 74260), phthalocyanine blue (C.I.
I. 74160), carbon black and the like. The content of the pigment in the colored photosensitive resin is 1
-30 mass% is preferable, and 5 is more preferable.
Is about 20% by mass.

The image-forming material used in the present invention can be obtained by applying a colored photosensitive resin solution onto a temporary support and then drying it. Further, if necessary, a thermoplastic resin layer and an intermediate layer can be provided. In that case, first, a thermoplastic resin layer solution is applied and dried to provide a thermoplastic resin layer, and then the thermoplastic resin layer is provided. A solution of an intermediate layer material consisting of a solvent that does not dissolve the thermoplastic resin layer is applied onto the resin layer and dried, and then a photosensitive resin layer is applied by using a solvent that does not dissolve the intermediate layer and dried. .

(Color Filter Manufacturing Method) Next, a process for manufacturing a color filter using the image forming material prepared by the above-mentioned method will be described. When a color filter is manufactured using the image forming material of the present invention, at least two steps can be selected depending on the method of forming the black matrix light shielding layer. One is a method of forming a black matrix light-shielding layer with a metal thin film.
The other is a method in which the image forming material is provided in the same manner as the red, green and blue pixels. When a metal thin film is used, it is preferable to form a black matrix light-shielding layer by a metal thin film before forming each pixel of red, green, and blue. On the other hand, when forming a black matrix light-shielding layer by transferring an image forming material, It is preferable to provide after each pixel of red, green, and blue is formed.

The black matrix light-shielding layer made of a metal thin film is formed by forming a metal Cr film having a thickness of 100 to 300 nm on a glass substrate having a thickness of about 1 mm by a method such as sputtering or vacuum deposition, and patterning it in a matrix by photolithography. Is obtained by As the metal thin film, various materials other than metal Cr can be used, but in view of the blackness of the film, the adhesion to the glass substrate, the denseness of the film, and the light blocking performance, the metal C is used.
r is preferred.

First, a photosensitive resin layer of an image forming material is attached to a transparent glass substrate (or a black matrix light shielding layer forming substrate of metal Cr) having a thickness of about 1 mm under heating and pressure. In this case, an undercoat such as a silane coupling agent may be preliminarily applied to the transparent glass substrate for the purpose of improving the adhesion between the photosensitive resin layer and the transparent glass substrate. A conventionally known laminator or a vacuum laminator can be used for bonding, and it is preferable to use an auto-cut laminator in order to further improve productivity. The temperature at the time of this bonding is 50 to 18 when measured on the image forming material side.
The temperature is 0 ° C, preferably 100 to 160 ° C. A polymerization inhibitor is usually added to the photosensitive resin layer for the purpose of suppressing undesired thermal polymerization, but the thermal polymerization cannot be completely suppressed, and after development, it remains in the non-image area on the glass substrate. A film is generated. This residual film is more likely to occur as the temperature during transfer, that is, the temperature of the photosensitive resin layer, increases. Usually, the generation starts when the temperature exceeds 100 ° C, is promoted when the temperature exceeds 110 ° C, and increases rapidly when the temperature exceeds 120 ° C. Generation of a residual film can be prevented by transferring at a low temperature at which thermal polymerization does not occur.

However, pixels are already formed during the transfer of the second and subsequent colors, and when the transfer temperature is low, it is difficult for the existing pixels to follow the surface irregularities, and air bubbles are entrained. Will occur. The photosensitive resin layer and the thermoplastic resin layer need to be sufficiently softened in order to improve the follow-up to the unevenness, and for this reason, the residual film is rapidly raised to 120 ° C. or higher. The surface temperature of the roller of the laminator is appropriately selected according to this condition. Transfer speed is usually 0.1m / min.
Perform at about 3 m / min. Considering mass productivity, usually, the maximum speed is selected within a range where air bubbles are not involved. This speed is appropriately determined by the physical properties of the photosensitive resin layer and the thermoplastic resin layer, the laminating temperature, the laminating pressure and the like.

After removing the temporary support, the photosensitive resin layer is exposed and developed through a predetermined photomask. At this time, it is preferable to peel off the thermoplastic resin layer together with the temporary support in order to obtain high resolution and shorten the developing time. The thermoplastic resin layer can be peeled off by controlling the balance of adhesion between the temporary support, the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer. It is also possible to perform exposure before peeling off the temporary support, and then peel off the temporary support for development.
In order to obtain high resolution, it is preferable to peel off the temporary support before exposure.

The development is carried out by a known method by immersing in a solvent-based or aqueous developer, particularly an alkaline aqueous solution, or spraying the developer from a spray, and further performing development treatment while applying ultrasonic waves. .

Next, in order to remove the development residual film in the non-image forming portion, a transparent glass substrate provided with a photosensitive resin layer which is patterned and developed in a development residual film removing liquid containing at least a surfactant. While brushing the surface, the same chemical solution is sprayed at high pressure. As the development residual film removing liquid used in the present invention, conventionally known cleaning liquids can be widely used, but among them, at least one anionic surfactant, and / or at least one nonionic surfactant, and An aqueous solution containing an alkaline agent is preferable because it has a great effect of removing the residual film.

When only water is used as the developing residual film removing liquid, the residual film cannot be removed sufficiently, and when the developing liquid itself is used, overdevelopment occurs and the peripheral portion of the pixel is side-etched. Will end up. Since this overdevelopment can be suppressed by reducing the concentration of the developing solution, it is possible to use this, but it is preferable to use a dedicated chemical solution.

In the present invention, the anionic surfactant contained in the residual developing film removing solution is not particularly limited. For example, carboxylic acid salts, sulfuric acid ester salts, sulfonic acid salts and the like can be mentioned. When forming a general-purpose color filter, a metal ion such as sodium may be contained, but in the case of a color filter for COA, it is preferable that the metal ion is not contained.
These anionic surfactants can be used alone or in combination of two or more.

In the present invention, the nonionic surfactant contained in the residual development film removing solution is not particularly limited. For example, ethers such as polyoxyethylene,
Examples thereof include esters such as polyoxyethylene and alkylamines. These anionic surfactants can be used alone or in combination of two or more.

In the developing residual film removing liquid of the present invention, it is preferable to add an alkaline agent for the purpose of enhancing the residual film removing effect. When forming a general-purpose color filter, an inorganic alkali such as sodium hydroxide may be contained, but C
Organic alkaline agents such as monoethanolamine and triethanolamine are preferred for OA applications. Further, an antifoaming agent may be contained for the purpose of suppressing foaming.

In the present invention, the concentration of the surfactant in the residual development film removing solution is preferably 0.005 to 1.0% by mass, and particularly preferably 0.01 to 0.5% by mass. Further, the concentration of the alkaline agent is preferably 0.005 to 5.0% by mass, and particularly preferably 0.01 to 3.0% by mass.

In the present invention, the above-mentioned residual film removing solution is sprayed on the substrate after development by a shower, or while the substrate is immersed in the residual film removing solution, brushing is performed and a similar chemical solution is applied. The residual film at the time of development can be completely removed by spraying at high pressure. It is difficult to completely remove the residual development film in the contact holes only by brushing, and cleaning of the glass surface of the substrate is usually insufficient in many cases by only high-pressure jetting. By performing both the brushing and the high-pressure jet, the inside of the contact hole and the substrate surface can be completely cleaned, and the residual film after development can be substantially removed. The chemical solution used for the high-pressure jet may be the above-mentioned development residual film removing solution for brushing as it is, but it is a chemical solution prepared separately and having a function of removing the development residual film containing at least a surfactant. May be. Further, either the brushing process or the high-pressure injection process may be performed first.

In the present invention, in the case of forming a color filter for COA use, it is used in the step of developing the pattern-exposed photosensitive resin layer, and in the step of brushing and high-pressure jetting. It is preferable that the chemical solution for removing the residual development film is substantially free of metal ions. If the developer and the residual film removing solution contain metal ions, various problems may occur in the operation of the TFT.

The brush used for the brushing of the present invention is not particularly limited, but a fiber roll brush made of nylon or acrylic, a disc brush made of PVA sponge or the like can be appropriately used. When using a fiber roll brush, it is preferable to use long fiber legs (at least 10 mm or more) and thin fiber diameters (100 μm or less). It is not preferable to use a brush having short bristle legs and a large fiber diameter because the pixels are scratched or the pixels are peeled off. The rubbing time varies depending on the developing device and the brush used, but for example, a roll brush having a fiber diameter of 50 μm and a bristle leg of 25 mm is used, and the rotation speed of the brush is 100 rpm for 1 second to 2 seconds.
It is about 0 seconds. This is the contact time of each part when the substrate is horizontally conveyed while the surface of the substrate lightly touches the tips of the brush while the brush is rotating. If the contact time is too short, the residual film cannot be sufficiently removed, and conversely, if it is too long, the pixels are scratched or peeled off, which is not preferable.

There are no particular restrictions on the specific processing conditions for the high-pressure jet of the present invention, and there are no restrictions on the given substrate shape, exposure pattern,
It can be appropriately selected according to the properties of the photosensitive substance, the properties of the residual film removing liquid, and the like. 20-50 degreeC is preferable and, as for the liquid temperature of the chemical | medical solution for high pressure injection, 25-40 degreeC is more preferable. The pressure of the high-pressure injection is preferably 5 to 10 MPa, more preferably 10 to 15 MPa. Generally, a higher chemical temperature and higher injection pressure can be expected to have a cleaning effect, but on the other hand, the risk of heat damage or pressure damage increases. Can be decided The distance between the substrate and the spray nozzle is also appropriately selected depending on the balance between the cleaning effect or efficiency and damage avoidance, but is generally preferably 50 to 200 mm, more preferably 80 to 150 mm. The substrate transfer speed is appropriately selected in consideration of the injection flow rate of the chemical solution, but in general, the transfer speed is 1 m from the viewpoint of improving productivity.
It is desirable to set the injection flow rate so as to maintain the conveyance speed of / minute or more.

For the high-pressure injection of the present invention, a commercially available high-pressure injection cleaning device (system) suitable for the purpose of the invention can be preferably used. As a commercially available high-pressure jet cleaning device (system) that meets this purpose, for example, Asahi Sunac Co., Ltd.
Ultra-high pressure micro jet precision cleaning system manufactured by HPM
JAF5400S ”, a bubble jet (R) system manufactured by Shimada Rika Kogyo Co., Ltd., and the like.

It is preferable that the brushing process and the high-pressure jetting process be performed in-line so that they can be performed immediately after development. When developing, brushing, and high-pressure jetting are performed by separate devices, it is necessary to stop the development by washing the photosensitive resin layer with water after the development.

The substrate which has been subjected to the brushing process and the high-pressure jetting process is washed with water and drained with an air knife or the like. Before the process of transferring the image forming material of the next hue is performed, the substrate is subjected to a heat treatment (post-baking). It is preferable to include either one or both of the steps of irradiating with light having a wavelength range capable of curing the patterned photosensitive resin layer.

To manufacture a color filter, red, green, blue, and black (black is unnecessary when the light-shielding layer is formed of a metal film) and four treatment processes are required.
The development processing is performed multiple times, four times for the second formed color image, three times for the second formed color image, and twice for the third formed color image. This results in the collapse of the pixel shape due to overdevelopment. This tendency becomes even stronger when brushing and high-pressure jetting are performed after development. Therefore, it is preferable to sufficiently cure the image by the above-described method (post-baking) after forming the image of each color. In the case of heat treatment, the temperature is in the range of 100 ° C. to 300 ° C., preferably 150 ° C. to 250 ° C., and the treatment time is 1 minute to 180 minutes after the temperature of the substrate reaches that temperature, preferably 5 minutes to 12 minutes.
It is in the range of 0 minutes.

As the heat treatment (post-baking) method, various conventionally known methods can be used. That is,
A method of housing a plurality of substrates in a cassette and processing them in a convection oven, a method of processing one by one with a hot plate, a method of processing with an infrared heater, and the like.

In the case of light irradiation, light having a wavelength range in which the photosensitive resin layer can be cured, and in the case of the present invention, light having a wavelength of 365 nm or 405 nm is irradiated (this may be hereinafter referred to as "post-exposure"). Irradiation may be from the imaged surface, the opposite surface, or both sides. Dose is one 5 mJ / cm ² or more, preferably 50 mJ / cm ² or more, more preferably 200 mJ / cm ² or more, but is no particular upper limit,
Considering manufacturing suitability, it is about 3000 mJ / cm ² or less. As the irradiation method, known techniques such as a method of collectively exposing light from an ultra-high pressure mercury lamp or a high-pressure mercury lamp one by one, a method of irradiating from above or below while conveying an image forming substrate by a conveyor, or from both, are known. Available.

The steps from the bonding of the image forming material to the heat treatment (or post exposure) are performed in red, green and blue.
If repeated for black, a color filter can be formed. Here, when a glass substrate having a light-shielding layer formed in advance with a metal thin film is used, the black image forming step can be omitted.

Further, if necessary, a protective layer for the purpose of physical and chemical protection and flattening of the color filter surface may be laminated on the color filter. As the protective layer, a resin film of acrylic, urethane, silicone or the like, or a highly transparent film such as a metal oxide of silicon oxide or the like is used.
In addition to spin coating, roll coating, printing, etc., it can be formed by transfer like the above-mentioned image forming material. In addition, an inorganic film such as a metal oxide can be provided by a sputtering method, a vacuum vapor deposition method or the like.

[0045]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In this example, unless otherwise specified,
All “parts” and “%” represent “parts by mass” and “mass%”.

Example 1 A coating solution of the following formulation (A) was applied onto a temporary support of a polyethylene terephthalate (PET) film having a thickness of 75 μm and dried to form a thermoplastic resin layer having a dry film thickness of 15 μm. Provided. This resin layer is
When sequentially forming a plurality of layers of pixels by lamination, it plays a role of preventing bubbles from being mixed due to the presence of already formed pixels.

[0047]   <Thermoplastic resin layer formulation: A> ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate  Rate / methacrylic acid copolymer (copolymerization molar composition ratio = 55 / 11.7 / 4.5 /28.8, mass average molecular weight = 80000) 4.5 Department Styrene / acrylic acid copolymer (copolymerization mass composition ratio = 70/30, mass average content Child quantity = 80000) 10.5 copies ・ 7 parts of "BPE-500" manufactured by Shin Nakamura Chemical Co., Ltd. ・ F177P (fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.26 parts ・ Methyl ethyl ketone 18.6 parts ・ Methanol 30.6 parts ・ 1-Methoxy-2-propanol 9.3 parts

Next, a coating solution of the following formulation (B) was applied onto the thermoplastic resin layer and dried to form an intermediate layer having a dry film thickness of 1.6 μm. This layer functions as a barrier layer for preventing the colored layer formed next on the layer and the thermoplastic resin layer formed previously from being mixed with each other. It also functions as an oxygen barrier film.

[0049]   <Intermediate layer formulation: B> 13 parts of polyvinyl alcohol ("PVA205" manufactured by Kuraray Co., Ltd.) ・ Polyvinylpyrrolidone (“PVP-K30” manufactured by Gokyo Sangyo Co., Ltd.) 6 parts ・ Methanol 173 parts ・ Water 211.4 copies

Red (for the R layer), green (for the G layer), and blue (for the B layer) having the formulations shown in Table 1 below are provided on the temporary support provided with the thermoplastic resin layer and the intermediate layer. Three-color photosensitive resin solutions are applied and dried to obtain a dry film thickness of 2 μm.
To form a colored photosensitive resin layer.

[0051]

[Table 1]

Furthermore, a thickness of 1 is formed on the colored photosensitive resin layer.
A 2 μm polypropylene covering film was attached to prepare red, blue and green image forming materials. Using this image-forming material, a color filter was produced by the method described below.

First, the washed thickness of 0.7 mm is 400 m.
An m × 300 mm array substrate (a transparent glass substrate on which TFT elements are formed, almost the entire surface is covered with SiNx, and Al electrodes are formed at the positions that should be contact holes for each pixel) is a silane cup. After dipping for 30 seconds in a 0.3% aqueous solution of a ring agent (“KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd.), rinsed with pure water for 30 seconds and dried with an air knife. This operation is to improve the adhesion between the colored photosensitive resin layer and the glass substrate.

Next, while peeling off the covering film of the above-mentioned red image forming material (transfer film), the surface of the colored photosensitive resin layer was directed toward the transparent glass substrate heated to 100 ° C. and a laminator (manufactured by Somar Co., Ltd.). A cut laminator “ASL-24”) was used to heat (130 ° C.) and pressurize (2 MPa) to bond them together. Then, after the substrate was at room temperature, it was peeled at the interface between the temporary support and the thermoplastic resin layer while removing the charge on the peeling interface and the substrate surface with an ionizer, and the temporary support was removed.

Next, the film is exposed to light through a predetermined photomask and developed, and then the formed image surface is brushed with a roll brush made of acrylic fiber in a residual film removing solution shown below, and the product is manufactured by Asahi Sunac Co., Ltd. Using the ultra-high pressure micro jet precision cleaning system "HPMJAF5400S", the same residual development film removing solution is sprayed at a pressure of 10 MPa, washed with water, drained, post-exposed, and heat-treated in a convection oven to form a transparent glass substrate. Then, a red pixel pattern was formed. A contact hole of 20 μφ is formed in the pixel at an electrode position on the array substrate.

[0056]   <Development residual film remover formulation> ・ Triethanolamine 1.5g -Takemoto Yushi Co., Ltd. "Pionin D-3120P" 0.075g ・ Pure water 98.43g

Subsequently, the green image forming material is laminated on the glass substrate on which the red pixel pattern is formed, and peeling, exposure, development, brushing, high pressure jetting, washing, draining and heat treatment are performed. , A green pixel pattern was formed. Further, the same process was repeated with the blue image forming material to form a color filter on the transparent glass substrate. The conditions of the above-mentioned transfer, exposure, development, brushing, high-pressure jetting, and heat treatment are as shown in Table 2 below.

[0058]

[Table 2]

The supplementary explanation of the items described in Table 2 and other conditions are as follows. (1) Development 1 is a development for dissolving and removing the thermoplastic resin layer and the intermediate layer, and triethanolamine 1 is used as a developing solution.
% Aqueous solution was used for shower development at 33 ° C. (2) In Development 2, the colored photosensitive resin layer was developed, and shower development was performed at a temperature of 33 ° C. using the following formulation solution as a developing solution. <Developer formulation> -Monoethanolamine 6.11 g- "Pionine D-3120P" manufactured by Takemoto Yushi Co., Ltd. 6.8 g- "WTC-1146" manufactured by Asahi Denka Co., Ltd. 0.1944 g-Acetic acid 3.57 g・ Pure water 469.55 g (3) Brushing treatment was performed while showering the residual film removal solution at a temperature of 33 ° C.
The acrylic roll brush of No. 1 was rotated at 100 rpm and the substrate transfer speed was 2 m / min. (4) The HPMJ (high-pressure jet) treatment was performed at a temperature of 33 ° C. with a residual developing film removal liquid at a substrate-nozzle distance of 100 mm, a substrate transport speed of 2 m / min, and a pressure of 10 MPa. (5) Post exposure is 500mJ / c with high pressure mercury lamp
m ² irradiation. (6) The heat treatment indicates the time after the substrate reaches the set temperature (220 ° C.) in the convection oven.

With respect to the color filter treated under the above-mentioned conditions, there was no peeling of the surface of the photosensitive resin layer from the step of adhering the image forming material to the step of peeling the temporary support, and a color filter could be manufactured. Further, in a test by irradiating with a projector lamp in a dark room, a non-development film was not substantially seen in the non-image forming part, and there was no stain, scratch, or peeling of the image even under a microscope observation, which was satisfactory. . Further, there was substantially no development residual film on the electrode surface in the contact hole of each pixel, and after that, conduction with the ITO pixel electrode formed on the pixel was completely obtained.

[Comparative Example 1] The same as Example 1 except that the process of brushing in the residual developing film removing solution and the process of jetting at a high pressure using an ultrahigh pressure micro jet precision cleaning system were omitted. A color filter was produced under the same conditions. As a result, in the process of peeling the temporary support after laminating the third color blue (B) image forming material, the colored photosensitive resin layer surface is peeled off over almost the entire surface, which can be used as a color filter. Did not become.

[Comparative Example 2] A color filter was produced under the same conditions as in Example 1 except that the treatment of jetting at high pressure using the ultrahigh pressure microjet precision cleaning system in Example 1 was omitted. As a result, the colored photosensitive resin layer surface was not peeled off, but a strong undeveloped film remained on the electrode in the contact hole, and the electric resistance with the ITO pixel electrode formed on the pixel became infinite thereafter. It was

[Comparative Example 3] In Example 1, except that the process of brushing in the residual developing film removing solution was omitted.
A color filter was produced under the same conditions as in Example 1. As a result, in the step of peeling the temporary support after laminating the third color blue (B) image forming material, the surface of the colored photosensitive resin layer having an area of about 1/3 is peeled off, which can be used as a color filter. Was not.

[0064]

According to the present invention, the colored photosensitive resin layer provided on the temporary support is transferred to a transparent glass substrate, the temporary support is peeled off, and pattern exposure and development are carried out, and then at least the surface activity is obtained. By repeating the step of brushing in the residual developing film removing solution containing an agent and spraying the same residual developing film removing solution at high pressure with respect to the image forming material colored in a different hue, the non-image forming part of the transparent substrate is formed. It is possible to manufacture an excellent color filter that has substantially no residual film after development and has no peeling of the surface of the colored photosensitive resin layer. In particular, when a COA color filter is manufactured, a development residual film does not substantially exist in the contact hole, and complete conduction can be obtained with the ITO pixel electrode formed on the pixel thereafter.

Claims (4)

[Claims] 1. A process for producing a color filter by transferring a plurality of colored photosensitive resin layers onto a transparent substrate,
(1) a step of bringing the colored photosensitive resin layer on the temporary support into close contact with the image forming material while heating the transparent resin on the transparent substrate; and (2) peeling off the temporary support. A step, and (3) a step of pattern-exposing the photosensitive resin layer,
(4) a step of developing the photosensitive resin layer, and (5) brushing the surface of the transparent substrate having the patterned and developed photosensitive resin layer in a residual development film removing solution containing at least a surfactant. And a step of ejecting the same chemical liquid at high pressure, and (6) repeating the steps (1) to (5) for image forming materials colored in different hues. Method for manufacturing color filter. 2. The method for producing a color filter according to claim 1, wherein the developing solution and the residual developing film removing solution do not substantially contain metal ions. 3. The method for producing a color filter according to claim 1, wherein the development residual film removing liquid comprises an anionic surfactant, and / or a nonionic surfactant, and an alkaline agent. 4. The method of manufacturing a color filter according to claim 1, wherein the transparent substrate is a TFT array substrate.