JP2003215813A - Developing material for color filter or structural material for liquid crystal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing method for a color filter or structural material for liquid crystal which produces less residues and is free of development unevenness even for a large-sized substrate. <P>SOLUTION: The developing method for the color filter or structural material for liquid crystal which includes a process of forming a photosensitive resin composition layer on a substrate, a process of pattern exposure, and a process of removing unnecessary parts by development includes at least one processing liquid supply means which supplies at least one kind of processing liquid among developing liquid, rinse liquid, and cleaning liquid to the substrate; and the processing liquid supply means is equipped with an introducing passage 14 having an intake 12 for introducing the processing liquid at one end and an introducing opening part 18 which is open to the substrate at the other end and a processing liquid supply member 20 which has many through holes is provided at the introducing opening part 18. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a color filter or a structural material for a liquid crystal, and more particularly to a method for developing a color filter or a structural material for a liquid crystal with less development residue.

[0002]

2. Description of the Related Art In a developing method used for producing a color filter or a structural material for liquid crystal, including a step of forming a photosensitive resin composition layer on a substrate, a step of pattern exposure, and a step of removing unnecessary portions by development, , Conventional, developer,
A dip development method in which the substrate is immersed in a treatment liquid such as a rinse liquid and a cleaning liquid for a predetermined time, a shower development method in which the treatment liquid is shower sprayed using a shower nozzle, and a spin development method in which the substrate or the shower nozzle is rotated. Have been used.

However, the dip developing method has a problem that a residue tends to remain after development because the processing liquid is in a substantially stationary state. In the shower development method, the residue can be effectively removed by the pressure of the shower, but when the size of the substrate increases, the amount of the processing liquid staying on the substrate increases, and the other processing liquid weakens the shower contact with the substrate to remove the residue. There was a problem that the removal efficiency deteriorates. In order to prevent such processing liquid from staying on the substrate, a spin developing method has been considered as a method in which the substrate is rotated and the processing liquid is discharged at any time by centrifugal force. However, in this spin development method, although the residue due to the delay due to the retention of the treatment liquid on the substrate is reduced, the centrifugal force does not work sufficiently near the center of the substrate, and residual acid near the center of the substrate cannot be removed. There is a problem in that the developing property of this portion becomes insufficient and uneven development occurs because the developing property of this portion is different from the surroundings.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for developing a color filter or a structural material for liquid crystal which has a small amount of residue even on a large substrate and has no uneven development.

[0005]

The method for developing a color filter or a structural material for a liquid crystal of the present invention comprises (1) a step of forming a photosensitive resin composition layer on a substrate,
A development method used for manufacturing a color filter or a structural material for liquid crystal, which includes a step of pattern exposure and a step of removing an unnecessary portion by development, wherein at least one processing solution of a developing solution, a rinsing solution and a cleaning solution is applied to the substrate. An introduction passage including at least one processing liquid supply means for supplying, the processing liquid supply means having an introduction port for introducing the processing liquid at one end, and an introduction opening opening at the other end toward the substrate. A method for developing a color filter or a structural material for a liquid crystal, comprising a treatment liquid supply member having a large number of through holes in the introduction opening. (2) A plurality of the introduction passages are arranged side by side in a direction perpendicular to the relative movement direction with respect to the substrate and / or the relative movement direction with the substrate, and the treatment liquid supply member is provided in each of the plurality of introduction passages. (1) The method for developing a color filter or a structural material for a liquid crystal according to (1). (3) A discharge passage is formed corresponding to one of the introduction passages or each of the introduction passages, the discharge passage having a discharge opening for discharging the processing liquid after passing through the substrate surface to the outside. A method for developing a color filter or a structural material for liquid crystal according to (1) or (2). (4) The treatment liquid supply means has an introduction passage having an introduction port for introducing the treatment liquid at one end, and a discharge port having one end for discharging the treatment liquid after passing through the substrate surface to the outside. A passage is formed, and an introduction opening and a discharge opening that open toward the substrate are provided at the other ends of the introduction passage and the discharge passage, respectively. The method for developing a color filter or a structural material for a liquid crystal according to any one of (1) to (3), which includes a nozzle provided with a member having a through hole. (5) An ultrasonic vibration applying means for applying ultrasonic vibration to the processing liquid on the substrate to be processed is provided between the introduction opening and the discharge opening (3) or (4) A method for developing a color filter or a structural material for liquid crystal according to the above. (6) The method for developing a color filter or a structural material for liquid crystal according to any one of (1) to (5), characterized in that the treatment liquid supply means includes a shower nozzle.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described in detail below. The present invention comprises a step of forming a photosensitive resin composition layer on a substrate, a step of pattern exposure,
It is a developing method used for manufacturing a color filter or a structural material for liquid crystal, which includes a step of removing an unnecessary portion by developing.

<Step of Forming Photosensitive Resin Composition Layer on Substrate> Examples of means for forming the photosensitive resin composition layer on the substrate include coating method and transfer method. —Coating method— The prepared photosensitive resin composition solution is applied to the surface of the substrate, and the solvent is removed by heating and drying in an oven to form a coating film of the photosensitive resin composition. The method for applying the composition solution is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method,
Various methods such as an extrusion coating method, a curtain coating method, a die coating method, a wire bar coating method and a knife coating method can be adopted. The conditions for prebaking vary depending on the type of each component, the usage ratio, etc., but are usually at 60 to 110 ° C. for about 30 seconds to 15 minutes.

—Transfer Method of Photosensitive Thermosetting Resin Layer Transfer Material— After forming a photosensitive resin layer transfer material by coating and drying the photosensitive resin composition solution of the present invention on a temporary support, it is formed on a substrate. The photosensitive layers are laminated and transferred under heat and pressure by a laminator. This method is particularly effective when manufacturing a color filter. The temperature of the heat press roll at the time of transfer is 50 ° C to 150 ° C.
Therefore, the linear pressure at the time of crimping is preferably 5 Kg / cm to 25 Kg / cm. The lamination speed is 0.
2 m / min to 4 m / min is preferable. Particularly preferable conditions are a heating and pressure roll temperature of 130 ° C. to 140 ° C., a linear pressure at the time of pressure bonding of 10 Kg / cm to 15 Kg / cm, and a conveying speed of 1 m / min to 3 m / min.

<Pattern exposure step> The formed coating film is irradiated with light through a mask having a predetermined pattern and then developed by a developing solution to form a pattern. The light used here is, for example, g-line (wavelength 43
6 nm), i-line (wavelength 365 nm) and continuous and / or bright line ultraviolet rays from known light sources such as ultra-high pressure mercury lamp, xenon lamp, carbon arc lamp and argon laser, far ultraviolet ray such as KrF excimer laser, synchrotron. Examples thereof include X-rays such as radiation and charged particle beams such as electron beams. Among these, g-rays and i-rays and ultraviolet rays in the 300 nm to 440 nm region containing them are preferable. As described in JP-A-6-59119, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used together.

<Step of Removing Unnecessary Parts by Development> As the developing solution for the above-mentioned photosensitive resin layer, the developing solution is an inorganic alkaline solution such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, triethylamine or the like. Alkylamines, alcoholamines such as triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide are used. A known surfactant can be further added to the developer.
The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

The present invention is a method for developing a color filter or a structural material for liquid crystal, which includes at least these steps. In addition to the step of forming a photosensitive resin composition layer on a substrate, the step of pattern exposure, the step of removing unnecessary portions by development, 1) a rinse step using pure water or the like, 2)
In addition to pure water, a cleaning step using ultrapure water, electrolytic ion water, ozone water, hydrogen water, etc. may be included.

The color filter is preferably formed by a transfer method. When a color filter is formed by this transfer method, it is desirable that a temporary support be provided with a thermoplastic resin layer and an oxygen blocking film, and that the oxygen blocking film be provided with a photosensitive resin layer. In this way, an integrated film in which the temporary support, the thermoplastic resin layer, the oxygen barrier film, and the photosensitive resin layer are integrated is produced for each color, and the integrated film for each color is transferred to form a color filter. . Examples of this type of integrated film include JP-A-2000-35591, JP-A-2000-39024, JP-A-2000-89025, JP-A-2000-106276, and JP-A-2000-27337.
0, JP-A-2000-310772, JP-A-2000-31
4804, JP 2000-19766, JP 200-3
3615, JP 2001-33616 A, JP 2001-A1
42119, JP 2001-71563 A, JP 2001 A
-83694, JP 2001-116913 A, JP 20
01-142065, JP 2001-159709 A, JP 2001-208908 A, JP 2001-21407 A.
7, JP 2001-221909 A, JP 2001-22 A
3472, JP 2001-228469 A, JP 2001 A
The compositions described in Examples and the like of −242315, JP 2001-272523 A and the like can be used.

In recent years, there is an increasing need for forming a fine structural material for liquid crystal having a resolution of about 5 to 20 microns and a height of about 1 to 10 microns. Examples of the structural material for liquid crystal include micro condenser lenses for color filters, spacers for liquid crystal display panels, high aperture type (hereinafter sometimes referred to as “HA type”) liquid crystal display insulating films, and color filters. On-array method (hereinafter may be referred to as “COA method”) Insulating film for liquid crystal display, alignment dividing structure on color filter, liquid crystal alignment control material for plasma addressed liquid crystal display, flattening on color filter Overcoat materials for use. A structural material for liquid crystal particularly effective for the developing method of the present invention is a spacer for a panel or a liquid crystal orientation division control material.

The present invention includes at least one processing liquid supply means for supplying at least one processing liquid of a developing liquid, a rinsing liquid and a cleaning liquid to the substrate when developing the above-mentioned color filter or liquid crystal structural material. The treatment liquid supply unit has an introduction passage having an introduction port for introducing the treatment liquid at one end, and an introduction opening opening at the other end toward the substrate, and a large number of through holes are formed in the introduction opening. It is characterized in that the processing liquid supply member has.

Hereinafter, the processing liquid supply means will be simply referred to as an extrusion nozzle. A preferred embodiment of the extrusion nozzle will be described with reference to FIG. FIG. 1 (A) is a schematic configuration diagram seen from a plane orthogonal to the substrate transfer direction, and FIG.
[Fig. 3] is a schematic configuration diagram viewed from the surface of the substrate in the carrying direction. Figure
In 1, the extrusion nozzle 10 is provided with an introduction passage 14 having an introduction port 12 for introducing the treatment liquid at one end, and an introduction opening 18 that opens toward the substrate 16 at the other end. A treatment liquid supply member 20 having a large number of through holes is provided. The treatment liquid supply member 20 may be made of a porous material and has a large number of communication holes. The communication holes may be slit-shaped or thin communication holes. Further, it may be a porous plate, a sintered body of granular material, or porous ceramics. Further, a porous molded article of resin or a hard sponge may be used. The processing liquid supply member shown in FIG. 1B shows a mode in which a large number of slits are provided in parallel with the substrate 16 transport direction. As the porous material, a fluororesin, a plastic such as polyethylene, a metal such as SUS, a ceramic such as alumina and silicon oxide, a metal oxide such as a plastic TiO ₂ which has been hydrophilically treated, and the like can be used.
Particularly when the treatment liquid is a rinse liquid or a cleaning liquid, the porous material forming the treatment liquid supply member 20 is preferably a hydrophilic material.

The extrusion nozzle 10 may be arranged in a relative movement direction with respect to the substrate 16 or in a direction orthogonal to the relative movement direction with respect to the substrate 16. Therefore, the extrusion nozzle 10 may be fixedly arranged over the width direction of the substrate conveyed by the conveyor 22, or may be arranged movably along the width direction of the substrate conveyed. Further, the extrusion nozzle 10 may have a plurality of extrusion nozzles 10 fixedly arranged along the conveyance direction of the substrate 16, or may be arranged movably along the conveyance direction of the substrate 16.

When this extrusion nozzle 10 is used, the processing liquid W is supplied onto the substrate 16 through a large number of through holes formed in the processing liquid supply member 20 made of a porous material. At this time, the treatment liquid W is supplied almost uniformly from the entire surface of the treatment liquid supply member 20 facing the substrate 16 as indicated by an arrow in FIG. 1B, and the substrate has a substantially uniform flow velocity. It is uniformly and rapidly supplied to a wide area on 16, and unnecessary portions due to development can be efficiently removed.

In the present invention, the treatment liquid supply means includes an introduction passage having an introduction port for introducing the treatment liquid at one end, and a discharge passage for discharging the treatment liquid after passing through the substrate surface at one end. A discharge passage having an outlet is formed, and an introduction opening and a discharge opening opening toward the substrate are provided at the other ends of the introduction passage and the discharge passage, respectively. Including a nozzle provided with a member having a large number of through holes in the part, and
It is desirable that an ultrasonic vibration applying unit for applying ultrasonic vibration to the processing liquid on the substrate to be processed is provided between the introduction opening and the discharge opening.

The means including the processing liquid supply means and the ultrasonic vibration applying means will hereinafter be simply referred to as an ultrasonic extrusion suction nozzle. A preferred embodiment of the extrusion suction nozzle with ultrasonic waves will be described in detail with reference to FIG. Figure 2
FIG. 2A is a schematic configuration diagram viewed from a plane orthogonal to the substrate transport direction, and FIG. 2B is a schematic configuration diagram viewed from the substrate transport direction surface. In FIG. 2, an inlet passage 14 having an inlet 12 for introducing the processing liquid W at one end, and an outlet passage 26 having an outlet 24 for discharging the processing liquid W after passing through the substrate surface to the outside at one end. Is formed, and an introduction opening 18 and a discharge opening 28 that open toward the substrate are provided at the other ends of the introduction passage 14 and the discharge passage 26, respectively, and a large number of through holes are formed in the introduction opening 18. A treatment liquid supply member 20 having a plurality of through holes and a nozzle provided with a treatment liquid discharge member 30 having a large number of through holes in the discharge opening portion 28, and the introduction opening portion 18 and the discharge opening portion 28.
An ultrasonic oscillator 32 as an ultrasonic vibration applying means for applying ultrasonic vibration to the processing liquid on the substrate 16 to be processed is provided between and. In addition, in the discharge opening 28,
A decompression pump (not shown) is connected and the suction pressure by the decompression pump is controlled to control the difference between the pressure of the processing liquid in contact with the atmosphere at the introduction opening 18 and the atmospheric pressure to process the substrate 16. The supply of the liquid W and the discharge of the used processing liquid W from the substrate 16 side can be ensured.

A cable (not shown) is connected to the ultrasonic oscillator 32 so as to control the ultrasonic oscillator 32, and the ultrasonic oscillator 32 is parallel to the substrate 16 to be conveyed. It is preferable to have a predetermined angle θ with respect to the plate material (vibration surface) 34 arranged. By providing the angle θ, the ultrasonic wave 32 can be protected by suppressing the megasonic reflected wave from the substrate 16. Also,
The liquid film existing between the substrate 16 and the vibrating surface is held by the pressure control (bomb suction + surface tension) of the processing supply line.

The gap between the plate material (vibration surface) 34 and the substrate corresponds to the thickness of the treatment liquid W, is preferably 0.1 to 30 mm, more preferably 0.2 to 20 mm, and the vibration frequency is 15 to 15. 40 KHz is preferable, more preferably 18
~ 25 KHz.

In the embodiment shown in FIG. 2, the processing liquid W is supplied from the processing liquid supply member 20 when the substrate 16 approaches the lower part of the processing liquid supply member 20, but the ultrasonic transducer 32 does not operate. When the substrate 16 further moves and passes below the ultrasonic transducer 32, the discharge pump is operated to discharge the processing liquid W supplied onto the substrate 16 from the processing liquid supply member 20 from the processing liquid discharge member 30. Let At this stage, the processing liquid W comes to steadily flow on the substrate 16. Therefore, by operating the ultrasonic transducer 32 at the same time, unnecessary portions on the surface of the substrate 16 are efficiently processed with a very small amount of processing liquid. Can be removed.

FIG. 3 is a schematic block diagram showing an embodiment of a developing device for carrying out the developing method of the present invention, and FIG. 4 (A) is a developing device for carrying out the developing method of the present invention. It is a schematic block diagram which shows other embodiment of this. Further, FIG. 4B is a schematic configuration diagram of a conventional developing device. Figure 3
In this developing device, a front chamber 34, a developing tank 36, an air knife chamber 38, a rinse tank 40, a residue removing tank 42, an air knife chamber 44, and a rear chamber 46 are provided. It is designed to be transported. The developing tank 36 is provided with a shower mechanism 36A, and the rinse tank 40 is also provided with a shower mechanism 40A. The residue removing tank 42 is provided with the above-described extrusion suction nozzle 43 with ultrasonic waves.

In FIG. 4 (A), the developing device includes a front chamber 34, a first developing tank 48, a first rinsing tank 50, a second developing tank 52, a second rinsing tank 54, a third developing tank 56, and a third developing tank 56. Three rinse tanks 58, residue removal tank 42, air knife chamber 44, rear chamber 4
6 is provided, and each rinse tank is provided with a shower mechanism. The second developing tank 52 is provided with the above-mentioned extrusion nozzle 10, the third developing tank 56 is provided with an ultra-high pressure jet 57, and the residue removing tank 42 is provided with the above-mentioned ultrasonic-applied suction suction nozzle 43. Has been.

In the apparatus shown in FIGS. 3 and 4 (A), there is no particular restriction on the location of the ultrasonic extrusion extrusion suction nozzle 43, but it is effective to provide it after the development step and the rinse step are completed. is there. Generally, the processing liquid is supplied to the substrate by a shower or the like. A shower or the like aims to improve the processability by causing a processed droplet, which has gained kinetic energy due to its protruding pressure, to collide with the substrate surface.
When the processing liquid is supplied at a relatively high flow rate, processing unevenness is often caused. In particular, this processing unevenness becomes more remarkable as the substrate size increases. It is necessary to effectively and uniformly perform development, cleaning, and residue removal regardless of the substrate size.

When the processing liquid is supplied by the extrusion nozzle of the present invention, processing unevenness can be reduced. Further, if a suction nozzle (a discharge passage having a discharge port for discharging the processing liquid to the outside) is provided in parallel with the extrusion nozzle, processing unevenness does not occur at all. Further, by providing ultrasonic vibration applying means between the extrusion nozzle and the suction nozzle, it is possible to enhance the effects such as cleaning. In the developing tank, the shower pressure is 1.0 kgf / cm ^{2 to} 2.0 kgf /
The developing solution is sprayed in a shower in the range of cm ² , and the unexposed portion of the colored photosensitive resin composition is dissolved and removed.

In the rinse tank, for example, a protrusion pressure of 1.0 kgf / cm ^{2 to} 2.0 k is provided by a shower mechanism.
Pure water is sprayed in a shower shape in the range of gf / cm ² to remove most of the remaining colored photosensitive resin composition that could not be completely dissolved and removed in the developing tank. In the residue removal tank, pure water is supplied to the surface of the substrate while applying ultrasonic waves to the substrate surface by the extrusion suction nozzle with ultrasonic waves, and the residue that cannot be completely removed in the rinse tank is removed. In addition to pure water, ultrapure water, electrolytic ion water, ozone water, hydrogen water, etc. are used for removing the residue. Further, a cleaning liquid containing a surfactant or an alkali may be used for removing the residual passage. If necessary, a rinse tank with pure water is provided after the residue removing tank. Even in the case of a shower, an ultra-high pressure jet (Japanese Patent Laid-Open No. 10-92707, Japanese Patent Laid-Open No. 11-333387) that operates at a relatively small flow rate has less process unevenness, and is effective when used in combination with the present invention.

When forming an image with a colored material such as a color resist, or when forming an image having a relatively large thickness such as a structural material for liquid crystal, supplying a developer by a shower causes the image There is a problem that the cross section of the tape has a reverse taper shape, and the residue is likely to remain.

When the developing solution is supplied by the extrusion type nozzle of the present invention, the sectional shape of the image is improved. If a suction nozzle (a discharge passage having a discharge port for discharging the processing liquid to the outside) is provided in parallel with the push-out nozzle, uneven development will not occur at all. Further, after passing through the developing tank, the development residue is removed by an ultra-high pressure jet (JP-A-10-92707, JP-A-11-333387), an extrusion suction nozzle with an ultrasonic wave, a high pressure shower, an ultra high pressure jet, a cleaning brush or the like. Then, it is possible to obtain an image having a good cross-sectional shape without any residue.

In the present invention, as described above, the color filter or liquid crystal structure capable of removing the residue without unevenness regardless of the position of the plate and the size of the substrate and obtaining an image with a good cross-sectional shape. We can provide wood.

[0031]

[Examples of color liquid resist] <Example 1> As a transparent substrate, non-alkali glass manufactured by Corning Incorporated was used. Fuji Film Olin Co., Ltd. product name color mosaic, product number CRY-7 on this glass plate
000 was applied by a spinner to obtain a coating film of 1.5 μm. An exposure of about 200 mj / cm ² was performed through a photomask with a 3 KW ultra-low pressure mercury lamp. Next, the developing device 1 of the present invention was charged. The discharge pressure of the shower mechanism of the developing tank was 2.0 kgf / cm ^2, and an alkaline developer at 20 ° C. was showered and sprayed from the substrate side to dissolve and remove the colored photosensitive resin composition in the unexposed area. As an alkaline developer, sodium carbonate 0.14% by mass, sodium hydrogencarbonate 0.05% by mass, manufactured by Kao Corporation, anionic surfactant "Perex" 0.88% by mass, manufactured by Kao Corporation,
Nonionic Wetting Penetrant "Emulgen L-40" 0.65
A liquid prepared by mixing mass% and pure water 98 mass% was used. Next, in the rinse tank, pure water having a discharge pressure of 2.0 kgf / cm ² was sprayed in a shower shape by a shower mechanism to remove most of the remaining colored photosensitive resin composition that could not be completely dissolved and removed in the developing tank. Removed. Next, in the residue removal tank, pure water was supplied to the surface of the substrate by an extrusion suction nozzle with ultrasonic waves for cleaning. The color filter thus obtained was a good color filter having no residue of the colored photosensitive resin composition at any position other than the colored resin layer (colored pixel), that is, on the glass surface at any position of the substrate.

<Comparative Example 1> A color filter was prepared in the same manner as in Example 1 except that the ultrasonic suction extrusion nozzle of the residue removing tank (developing layer) was not operated. Residues of the colored photosensitive resin composition were left in places on the obtained color filter.

<Example 2> [Dry film type color resist side] (Preparation of dry film type color resist) Thickness 5 μm
m coating solution of polyethylene terephthalate film was sprayed with a coating solution of the following formulation HI and dried, and then a base fabric solution of the following formulation Pl was applied and dried, and the following photosensitive resin layer solution Kl , R1, G
1, B1, C1 are sprayed and dried, and a thermoplastic resin layer having a dry film thickness of 1.6 μm, an oxygen barrier film having a dry film thickness of 146 μm, and a dry film thickness of 4 μm (C1 is 6 μm) on the temporary support.
m) was provided as a photosensitive layer, and a protective film (12 μm thick polypropylene film) was pressure-bonded thereto. In this way, an integrated film including the photosensitive resin layer of the dry film color resist in which the temporary support, the thermoplastic resin layer, the oxygen barrier film, and the photosensitive layer are integrated is created, and the sample names of the respective films are used. Resin layer solution symbols Kl, Rl, Gl, Bl,
Using Cl, the integrated film Kl, Rl, Gl, B
1 and Cl.

[0034] Thermoplastic resin layer formulation Η1: ・ Vinyl chloride / vinyl acetate copolymer 300 parts by mass ・ Vinyl chloride-vinyl acetate-maleic acid copolymer 80 parts by mass ・ Dibutyl phthalate 90 parts by mass   (Methyl ethyl ketone was used as the solvent) Oxygen barrier membrane formulation P1: ・ Polyvinyl alcohol 180 parts by mass ・ Fluorine-based surfactant 8 parts by mass   (Water was used as the solvent)

[0035] Photosensitive resin layer solution K1: ・ Benzyl methacrylate / methacrylic acid copolymer 60 parts by mass ・ Pentaerythritol tetraacrylate 40 parts by mass ・ Michler's ketone 3 parts by mass -2- (o-chloropheel) -4,5-diphenylimidazole dimer                                                                 3 parts by mass ・ Carbon black dispersion 100 parts by mass       (Methyl ethyl ketone was used as a beach medium)

[0036] Photosensitive resin layer solution R1: ・ Benzyl methacrylate / methacrylic acid copolymer 13 parts by mass ・ Ventaerythritol hexaacrylate 38 parts by mass ・ Phenothiazine 0.8 parts by mass ・ 2-Trichloromethyl-5- (p-thrutylmethyl)                         -1,3,4-oxadiazole 3.1 parts by mass ・ 2,4,6-Tris [2,4-bis (methoxycarbonyloxy)]                       Phenyl] -1,3,5 triazine 3.3 parts by mass ・ 7- [2- [4- (3-Hydroxymethylpiveridino) -6]       -Diethylamino] triazylamino] -3-phenyl 15 parts by mass -C. I. Pigmentro red 254 dispersion 220 parts by mass     (Methyl ethyl ketone was used as the solvent)

[0037] Photosensitive resin layer solution G1: ・ Benzyl methacrylate / methacrylic acid copolymer 32 parts by mass ・ Pentaerythritol hexaacrylate 40 parts by mass ・ Phenothiazine 0.04 parts by mass ・ 2-Trichloromethyl-5- (p-thrutylmethyl)                   -1,3,4-oxadiazole 1.9 parts by mass * 7- [2- [4- (3-hydroxymethylbiperidino) -6]         -Diethylamino] triazylamino] -3-phenyl 13 parts by mass -C. I. Pigment Green 36 dispersion 160 parts by mass -C. I. Pigment Yellow 138 dispersion liquid 110 parts by mass     (Methyl ethyl ketone was used as the solvent)

[0038] Photosensitive resin layer solution B1: ・ Benzyl metatalylate / methacrylic acid copolymer 22 parts by mass ・ Pentaerythritol hexaacrylate 40 parts by mass ・ Phenothiazine 0.2 parts by mass ・ 2-Trichloromethyl 5- (p-thrutylmethyl)                       -1,3,4-oxadiazole 2 parts by mass ・ 2,4,6-Tris [2,4-bis (methoxycarbonyloxy)]                       Phenyl] -1,3,5 triazine 2.5 parts by mass -C. I. Pigment Blue 15: 6 dispersion 160 parts by mass     (Methyl ethyl ketone was used as the solvent)

[0039] Photosensitive resin layer solution C1: ・ Polymer solution 240 parts by mass   Styrene / maleic acid copolymer benzylamine modified product = 63/32 (molar ratio) ・ Dipentaerythritol hexaacrylate 200 parts by mass ・ Cyclohexanone 730 parts by mass -Photopolymerization initiator IRG184 (CAS947-19-3) 10 parts by mass         (Methyl ethyl ketone is added appropriately)

Amorphous silicon is used as a substrate for T
A TFT substrate on which FT was formed was used. UV this substrate
After washing and washing with pure water, silane cup-linda solution (N-1β
It was immersed in (aminoethyl) γ-aminopropyltrimethoxysilane (0.3% by mass aqueous solution) for 30 seconds, subsequently immersed in pure water for 30 seconds, and dried at 110 ° C. for 5 minutes. After peeling off the application film of the integrated film R1, laminating it on the tomb plate with a roll laminator, exposing it with a pattern of 20 mJ / cm ² , and developing it with the developing machine 2 of the present invention [apparatus shown in FIG. 4 (A)]. did. In the developing machine 2 of the present invention, first, the triethanolamine-based developer whose temperature is adjusted to 38 ° C. in the first developing tank is supplied to the substrate by the shower mechanism, and the non-plastic resin layer H
1 and the oxygen barrier film P1 were removed. Subsequently, in the second developing tank, a photosensitive resin layer was formed by using an alkali developing solution of 1% by mass of monoethanolamine, 0.3% by mass of acetic acid and 0.6% by mass of polyoxyethylene naphthyl ether, the temperature of which was adjusted to 33 ° C. Developed. The alkaline developer is supplied to the substrate by an extrusion nozzle. On the surface of the substrate, most of the unexposed portion was removed by the dissolving power of the alkali developing solution.
Subsequently, in the third developing tank, monoethanolamine 0.
An alkaline developer containing 1% by mass, 0.02% by mass of acetic acid, and 0.1% by mass of polyoxyethylene alkyl ether, the temperature of which was adjusted to 30 ° C., was supplied to the substrate by an ultrahigh pressure jet. At this time, the thinly exposed photosensitive resin layer that remained thinly in the unexposed portion of the substrate surface was completely removed regardless of the location of the substrate. In this way, the photosensitive resin layer was developed to obtain a patterning image. Next, after post exposure of 300 mJ / cm ² , 220 ° C.
After that, it was post-baked for 20 minutes to form a THF tomb plate with R pixels having contact holes. The integrated film G
Perform the same process using 1, B1 and K1, RCB
A TFT substrate having the pixels and the light shielding film K was prepared. Subsequently, an ITO layer was formed on this substrate and patterned to form a pixel electrode. Subsequently, the same process was performed using the integrated film C1 to complete a lower FT substrate having a spacer and a color filter. This TFT substrate is
No development residue was found at any position on the tomb plate, the cross section of the pixel was forward tapered, and there was no contact failure between each pixel electrode and the TFT.

Comparative Example 2 A TFT having a spacer and a color filter was carried out in the same manner as in Example 2 except that development was carried out using the developing device of the comparative example [device shown in FIG. 4 (B)].
The board is completed. With this TFT substrate, development residues were found in the latter half of the substrate. Further, the cross section of the pixel had a part having an inverse taper shape. In addition, the contact with a part of the TFT of the pixel electrode was defective.

[0042]

As described above, according to the present invention, the development residue can be efficiently removed with an extremely small amount of the processing liquid regardless of the size of the substrate, and a color filter without uneven development can be obtained. be able to. Further, it is possible to provide a structural material for liquid crystal having a good cross-sectional shape.

[Brief description of drawings]

1A and 1B show a preferred embodiment of an extrusion nozzle according to the present invention, FIG. 1A is a schematic configuration view as seen from a plane orthogonal to a substrate transport direction, and FIG. 1B is as seen from a substrate transport direction surface. It is a schematic block diagram.

2A and 2B show a preferred embodiment of an ultrasonic extruding suction nozzle according to the present invention, FIG. 2A is a schematic configuration view seen from a plane orthogonal to a substrate transport direction, and FIG.
It is a schematic structure figure seen from a conveyance direction side of a substrate.

FIG. 3 is a schematic configuration diagram showing a preferred embodiment of a developing device for carrying out the developing method of the present invention.

FIG. 4 (A) is a schematic configuration diagram showing another preferred embodiment of the developing device for carrying out the developing method of the present invention,
FIG. 1B is a schematic configuration diagram of a conventional developing device.

[Explanation of symbols]

10 Extrusion nozzle 12 entrance 14 Introduction passage 16 substrates 18 Introductory opening 20 Processing liquid supply member 22 Conveyor 24 outlet 26 Discharge passage 28 Discharge opening 30 Processing liquid discharge member 32 ultrasonic transducer 33 Plate material (vibrating surface) 34 anteroom 36 developing tank 36A shower mechanism 38 Air knife room 40 rinse tank 40A shower mechanism 42 Residue removal tank 44 Air knife room 46 Rear room 48 First developing tank 50 First rinse tank 52 Second developer tank 54 Second rinse tank 56 Third developing tank 58 Third rinse tank

Claims (6)

[Claims] 1. A development method used for producing a color filter or a structural material for liquid crystal, which includes a step of forming a photosensitive resin composition layer on a substrate, a step of pattern exposure, and a step of removing an unnecessary portion by development. And at least one processing solution supply means for supplying at least one processing solution of a developing solution, a rinsing solution and a cleaning solution to the substrate, and the processing solution supply means has an inlet for introducing the processing solution at one end. A color filter or a liquid crystal having an introduction passage having the same and an introduction opening opening to the substrate at the other end, and a treatment liquid supply member having a large number of through holes provided in the introduction opening. For developing structural materials for automobiles. 2. A plurality of the introduction passages are arranged side by side in a direction perpendicular to the relative movement direction with respect to the substrate and / or the relative movement direction with the substrate, and the treatment liquid supply member is provided in each of the plurality of introduction passages. The method for developing a color filter or a structural material for a liquid crystal according to claim 1, which is provided. 3. A discharge passage having a discharge opening for discharging the processing liquid after passing through the substrate surface is formed corresponding to one of the introduction passages or each of the introduction passages. The method for developing a color filter or a structural material for a liquid crystal according to claim 1 or 2, which is characterized in that. 4. The treatment liquid supply means has an introduction passage having an introduction port for introducing the treatment liquid at one end, and a discharge port for discharging the treatment liquid after passing through the substrate surface to the outside at one end. A discharge passage having the discharge passage is formed, and an introduction opening and a discharge opening opening toward the substrate are provided at the other ends of the introduction passage and the discharge passage, and the introduction opening and / or the discharge opening are provided. The method for developing a color filter or a structural material for a liquid crystal according to claim 1, further comprising a nozzle provided with a member having a large number of through holes. 5. An ultrasonic vibration applying means for applying ultrasonic vibration to the processing liquid on the substrate to be processed is provided between the introduction opening and the discharge opening. The method for developing a color filter or a structural material for liquid crystal according to 3 or 4. 6. The method for developing a color filter or a structural material for a liquid crystal according to claim 1, wherein the processing liquid supply means includes a shower nozzle.