JP2001228628A - Developing solution for developing photosensitive resin, image forming method, method for producing color filter, method for producing active matrix substrate with color filter and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing solution for developing a photosensitive resin having no adverse effect on a thin film transistor, etc., capable of stably forming a high definition image and excellent in aging stability and to provide an image forming method free of the lowering of developability due to a pH change in development and capable of stably forming a high definition image. SOLUTION: The developing solution contains an amine compound as a developing agent and has a pH adjusted to the range from (the pKa of the amine compound)-0.5 to (the pKa of the amine compound)+1.2. The pH adjustment is preferably carried out with at least one selected from among a mineral acid, an organic acid, gaseous CO2 and an aqueous carbonic acid solution and the concentration of alkali metal ions in the developing solution is preferably <=0.1 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a color filter,
Build-up substrate, developer used for developing a photoresist used for manufacturing a printed circuit board, an image forming method for forming an image by exposing and developing, a portable information terminal, a personal computer, a word processor, an amusement device, a television device, etc. Flat display, a display plate using a shutter effect, a door, a window, a method for manufacturing an active matrix substrate used for a liquid crystal display element used for applications such as walls, and a liquid crystal display element, for more information, such as a photoresist New developer useful for development,
The present invention relates to an image forming method using the developer, a method of forming a colored layer (color filter) directly on an active matrix substrate, and a liquid crystal display device including an active matrix substrate having the color filter.

[0002]

2. Description of the Related Art Conventionally, a liquid crystal display device has been manufactured by enclosing a liquid crystal material between an active matrix substrate and a glass substrate with a color filter. However, in recent years,
Due to demands such as improvement of the aperture ratio at the time of high definition, a part or all of a colored layer or a transparent layer which is a color filter provided on the glass substrate side (hereinafter, may be referred to as a “resin layer”). Attempts have been made to directly form the substrate on the active matrix substrate side.

[0003] In the case of a developer used in the field of semiconductors, generally a certain amount of alkali metal ions is contained, which is absorbed by a resin layer during development, and alkali metal ions remaining in the resin layer are converted into thin film transistors (TFTs). It is well known that this has an adverse effect on the operating characteristics of a semiconductor device such as simply “TFT”. Since a driving semiconductor element such as a TFT is formed on the active matrix substrate, it is necessary to eliminate the contamination of the substrate by the alkali metal in the developing solution during the developing process. Therefore, a sodium carbonate-based developing solution generally used for forming a color filter can not be used, and it is desired to develop an organic alkali developing solution which does not contain alkali metal ions such as sodium and potassium. I was

[0004] As the organic alkali developer, there is a developer such as tetramethylammonium hydroxide (TMAH) or choline which is generally used in electronic material applications. Therefore, it is difficult to develop a very fine pattern region of the photosensitive resin which has been finely patterned and exposed, so that the resolution cannot be secured, and the defect rate is large. In this case, if the alkali concentration is reduced for the purpose of adjusting the developing speed, the stability of the developing solution will be deteriorated, and the developing performance will be reduced at the time of manufacturing, making stable manufacturing difficult.

On the other hand, in the case of an alkali developing machine, particularly a shower-type alkali developing machine, since it has a high contact efficiency with the air inside the machine, it works as a kind of "gas absorbing device". There is also a problem that the developer is easily absorbed and the pH of the developing solution is lowered during the production, so that the developing performance is lowered. Usually, a strong base is used as a measure against pH lowering at the design stage of an alkaline developer, or a scheme is devised to reduce pH fluctuation by assembling a buffer system. For example, US Pat.
No. 5,396,63 discloses a technique for widening the pH range by adding a carbonate to a strong alkaline aqueous solution such as potassium hydroxide. However, this technique relates to an alkali developing solution containing an alkali metal, and as described above, cannot be used as a developing solution for an active matrix substrate.

As described above, when a resin film such as a color filter made of a resin layer is to be directly formed on the active matrix substrate side having a driving element such as a TFT, the semiconductor element provided on the substrate is required. A developing solution that can develop a resin layer on a substrate without adversely affecting the image, has a stable developing property with respect to the resin layer, and has excellent stability over time that can form a high-definition image pattern is still provided. It is not at present.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a developing solution which does not adversely affect semiconductor characteristics of a TFT element or the like and which can form a high-definition image pattern stably and has excellent stability over time. SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method capable of stably forming a high-definition image without a decrease in developability due to a change in pH during a developing process. Further, the present invention does not cause a decrease in developability due to a change in pH during the development processing,
An object of the present invention is to provide a method of manufacturing a color filter that stably forms a high-resolution colored image (color filter). Further, the present invention provides a method of manufacturing an active matrix substrate with a color filter capable of stably forming a high-resolution colored image on an active matrix substrate without considering adverse effects on semiconductor characteristics such as TFT elements. The purpose is to: An object of the present invention is to provide a high-resolution liquid crystal display element having excellent pattern accuracy at low cost.

[0008]

Means for solving the above problems are as follows. That is, <1> a developer for developing a photosensitive resin containing an amine compound as a developing agent, wherein the pH value is (p of the amine compound)
(Ka−0.5) ≦ pH ≦ (pKa of amine compound + 1.
A developer for developing a photosensitive resin, which is adjusted to the range of 2).

<2> The developer for developing a photosensitive resin according to <1>, wherein the pH value is adjusted by adding at least one selected from a mineral acid, an organic acid, carbon dioxide and an aqueous solution of carbon dioxide. <3> The developer for developing a photosensitive resin according to <1>, wherein the pH value is adjusted by blowing carbon dioxide gas. <4> The developer for developing a photosensitive resin according to any one of <1> to <3>, wherein the alkali metal ion concentration is 0.1 ppm or less.

<5> a step of forming a photosensitive layer containing a photosensitive resin capable of being alkali-developed on a substrate, a step of image-wise pattern-exposing the photosensitive layer on the substrate, and a developing process A step of forming an image, wherein the developing solution used in the developing process is a developer for developing a photosensitive resin according to any one of <1> to <4>. The image forming method is characterized in that:

<6> a step of forming a photosensitive layer containing a photosensitive resin capable of being alkali-developable on a substrate, a step of image-wise pattern-exposing the photosensitive layer on the substrate, and a developing process A process for forming an image, wherein the developing solution used in the developing process is the above <1> to <4>.
3. The method for producing a color filter according to claim 1, wherein the photosensitive layer further contains a colorant to form a colored image on a substrate.

<7> A step of forming a photosensitive layer containing at least a photosensitive resin which can be developed with an alkali and a colorant on an active matrix substrate, and patternwise exposing the photosensitive layer on the active matrix substrate imagewise And a step of forming a colored image on the substrate by a development process, and the developer used for the development process is used for developing the photosensitive resin according to any one of <1> to <4>. A method for producing an active matrix substrate with a color filter, which is a developer.

<8> At least an active matrix substrate with a color filter obtained by the method for manufacturing an active matrix substrate with a color filter according to the above <7>, and light arranged opposite to the active matrix substrate with a color filter. A liquid crystal display device comprising: a transparent counter substrate; and a liquid crystal material sealed between the color filter active matrix substrate and the counter substrate.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The developer for developing a photosensitive resin according to the present invention contains an amine compound as a developing agent, and the pH value is determined by the relationship with the pKa of the amine compound.
(PKa-0.5 of amine compound) ≦ pH ≦ (pKa of amine compound + 1.2), and the image forming method, color filter manufacturing method, and color filter of the present invention are further characterized in that: In a method for manufacturing an active matrix substrate with an image, an image (color filter) is formed using the developer for developing a photosensitive resin of the present invention. Further, a liquid crystal display element of the present invention includes an active matrix substrate with a color filter obtained by the method of manufacturing an active matrix substrate with a color filter of the present invention. Hereinafter, the developer for developing a photosensitive resin of the present invention will be described in detail, and throughout the description, an image forming method, a method of manufacturing a color filter,
The method of manufacturing an active matrix substrate with a color filter and the details of a liquid crystal display element will be clarified.

<Developer for developing photosensitive resin> The developer for developing photosensitive resin according to the present invention is capable of dissolving and developing a photosensitive resin used for forming an image (color filter), as described later. The aqueous solvent contains at least an amine compound as an organic alkali agent as a developing agent, and has a pH value adjusted to the range of the following formula in relation to the pKa of the amine compound. (PKa- of amine compound)
0.5) ≦ pH ≦ (pKa of amine compound + 1.2) Further, if necessary, other components such as acids and organic solvents are contained.

Examples of the amine compound include organic amine compounds such as monoethanolamine (aminoethanol), N-methylaminoethanol, N, N-
Dimethylaminoethanol, N, N-diethylaminoethanol, N, N-dibutylaminoethanol, N-methyl-N- (2-hydroxyethyl) aminoethanol, diethanolamine, triethanolamine, N-
(Β-aminoethyl) aminoethanol and the like. These amine compounds may be used alone or in combination of two or more.

The concentration of the amine compound in the developer is preferably 0.05 to 10 mol / l (liter), more preferably 0.08 to 5 mol / l, and 0.1 to 10 mol / l.
〜3 mol / l is most preferred. The concentration is 0.05
If it is less than mol / l, it is too dilute to perform sufficient development, resulting in poor development. If it exceeds 10 mol / l, overdevelopment occurs and sufficient resolution cannot be obtained,
Failures such as roughening of the film surface may occur.

Further, the pH of the developer for developing a photosensitive resin containing the above-mentioned amine compound in an aqueous solvent is adjusted within the range of the following formula in relation to the pKa of the amine compound as a developing agent. (PKa-0.5 of amine compound) ≦ pH ≦ (pKa of amine compound + 1.2) In a state within the above range, the fluctuation in pH of the developer itself is small, and a large decrease in developability can be effectively suppressed. Can be. Here, pKa is a value defined as “−log ₁₀ (ionization constant of conjugate acid)” (Physical and Chemical Dictionary (3rd edition),
Explanation of “pK” on p.1079, Iwanami Shoten Co., Ltd.).

The above pH range ((pKa-0.5) ≦ pH)
In order to adjust the pH of the developer to ≦ (pKa + 1.2)), a known method such as (a) a method of adding an acid as a neutralizing agent, and (b) a method of blowing an acidic gas into the developer is used. Can be. In particular, in the method of (a) adding an acid as a neutralizing agent and the method of (b) blowing an acidic gas, a buffer solution is formed by mixing an acid agent, and the buffering action causes the developer to come into contact with the outside air. It is also preferable from the viewpoint that the pH fluctuation can be effectively suppressed (improvement of stability over time), and (b) a method of blowing an acidic gas is more preferable.

In adjusting the pH, acids added as a neutralizing agent include mineral acids (inorganic acids) such as hydrochloric acid, sulfuric acid and nitric acid;
Organic acids such as citric acid, succinic acid, oxalic acid, acetic acid, ascorbic acid, and amino acids; aqueous solutions of carbonic acid; and the like, and acidic gases include carbon dioxide. Among the above acids and acid gases, in terms of affecting semiconductor elements such as TFTs,
Acetic acid and carbon dioxide are preferred. Phosphoric acid can also be used when there is no concern about adverse effects such as contact, contamination, and interaction with metals, semiconductor elements, and the like.

The method of blowing carbon dioxide or the like into the developer is not particularly limited, and a known method can be appropriately selected. Further, as the amount of the acid or acid gas added to the developer, the initial pH value of the developer to be set, that is,
Any amount may be used as long as it is finally adjusted within the range of (pKa of amine compound-0.5) ≦ pH ≦ (pKa of amine compound + 1.2). The pH value can be measured by, for example, a pH meter (manufactured by Toa Denpa Kogyo KK).

Conventionally, since a developer used for developing a photosensitive resin is generally an alkaline solution, after preparing a developer whose pH has been adjusted to a predetermined value, it absorbs carbon dioxide gas in the atmosphere during the development process. As a result, a large pH fluctuation from the initial pH value was caused, and as a result, the developing property tended to fluctuate greatly. Moreover, in order to adjust the development speed of the photosensitive resin,
When the concentration of the alkaline agent in the developing solution is reduced by dilution, the developing speed is extremely reduced, causing poor development, and it has been difficult to carry out stable development processing. On the other hand, when the pH value of the developing solution itself (initial setting value) is adjusted to around pKa of the developing agent in advance as in the present invention, the initial pH value is in the pH stable region of the developing solution which is an alkaline solution. In addition, the fluctuation in pH can be suppressed, and the temporal stability of the developer can be improved. That is, since the area where the pH change near pKa is gentle in the titration curve of the alkaline aqueous solution composed of the amine compound as the developing agent is used as the initial pH value of the developer,
This is because the effect of carbon dioxide absorbed from the atmosphere is small. Moreover, as described above, when adjusting to a predetermined initial pH value, by neutralizing with an acid agent (acid or carbon dioxide gas, etc.), a buffering action by the introduction of the acid agent can be obtained, and from the outside, It also contributes to the suppression of pH fluctuation due to the absorption of acid components. Therefore, even when the developer is circulated and agitated in the developing machine for a long time, it is possible to prevent a significant decrease in developability due to a decrease in the pH of the developer.

In the present invention, the alkali metal ion concentration in the developer is preferably 0.1 ppm or less. As described above, alkali metal ions present in the developing solution may adversely affect semiconductor characteristics such as thin film transistors (TFTs). Therefore, it is desirable that the concentration of the alkali metal ions in the developing solution be as low as possible. The alkali metal ion concentration refers to the total ion concentration of alkali metal ions such as lithium, sodium, and potassium. This ion concentration is determined by the atomic absorption method (I
It can be measured by the CP emission method (plasma emission spectrophotometry).

In a semiconductor process for forming a semiconductor element such as a TFT on an active matrix substrate, it is known that the lower the concentration of the alkali metal, the higher the quality of the TFT or the like. Generally, the quality is controlled to about 50 ppb. Have been. In the processing of the active matrix substrate after the formation of the TFT, the influence of the alkali metal is slightly suppressed by forming an inorganic protective film or the like on the TFT.

In the present invention, as described later, in the step of forming a photosensitive layer containing a photosensitive resin on an active matrix substrate, the concentration of alkali metal ions in the developer is preferably 1 ppb to 10 ppm,
2 ppb to 1 ppm is more preferable, and 10 ppb to 10 ppm
0 ppb is most preferred. If the concentration exceeds 10 ppm, it may cause a malfunction of a TFT or the like.

An aqueous solvent is used for the developing solution. In addition to water, a small amount of an organic solvent miscible with water can also be added. Examples of water-miscible organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ
-Butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. As the concentration of the organic solvent,
0.1 to 30% by weight is preferred.

Further, a known surfactant can be added to the developer. As the concentration of the surfactant,
0.01 to 10% by weight is preferred.

Organic amine compounds often impose an unpleasant working environment on workers due to their odor.
An organic amine compound which is a diamine compound and has a functional group capable of forming a hydrogen bond, such as a hydroxyethyl group or a hydroxypropyl group, introduced into the diamine site, the volatility of the compound itself is reduced, and odor generation is reduced. Is also useful in that it can also suppress

The developer for developing a photosensitive resin of the present invention can also be used for developing a photosensitive resin used for a so-called build-up substrate described in JP-A-9-244239. It is known that even in a build-up substrate having a laminated structure in which a copper wiring layer is sandwiched between insulating films, if alkali metal ions are mixed in and remain, insulation failure due to ion migration is caused. The developer of the present invention containing no alkali metal ion is very useful in this application. Furthermore, Japanese Patent Application No. 8-3
It is also suitable for developing a photosensitive resin used for a dry film resist for a printed circuit board described in Japanese Patent No. 31481.

As described above, the developer using an amine compound has a low alkali metal ion concentration, and particularly when used for a substrate provided with a semiconductor element such as a TFT, adversely affects the semiconductor characteristics of the TFT element and the like. Can be used without. Further, the pH of the developer is adjusted with respect to the pKa of the amine compound used as the developing agent (pKa- of the amine compound).
0.5) ≦ pH ≦ (pKa of amine compound + 1.2), the developing solution itself has excellent stability over time, and a high-definition image area can be stably developed with high resolution. .

<Image Forming Method> In the image forming method of the present invention, a step of forming a photosensitive layer containing a photosensitive resin which can be alkali-developed on a substrate (hereinafter, may be referred to as a "photosensitive layer forming step"). ), A step of imagewise pattern-exposing the photosensitive layer on the substrate (hereinafter, sometimes referred to as an “exposure step”), and a step of forming an image on the substrate by a development process (hereinafter, “image formation”). Process).
And, if necessary, other steps may be included, and the developing solution of the present invention is used in the developing treatment in the image forming step. Hereinafter, the steps will be described in order.

[Photosensitive Layer Forming Step] In the photosensitive layer forming step, a photosensitive layer containing a photosensitive resin that can be alkali-developed is formed on a substrate. If necessary, another layer such as an oxygen barrier film can be formed. (Photosensitive layer) The photosensitive layer is configured to contain at least a photosensitive resin, and if necessary, a polymerizable compound, a polymerization initiator, a surfactant, an adhesion aid, a coloring agent such as a dye or a pigment,
It may contain other components such as an ultraviolet absorber.

As the photosensitive resin constituting the photosensitive layer,
It can be appropriately selected from known ones.
All photosensitive resins described in -82262 can be used.
As the photosensitive resin, those which can be developed with an aqueous alkali solution and those which can be developed with an organic solvent are known. From the viewpoint of preventing pollution and ensuring work safety, those which can be developed with an aqueous alkali solution are preferable. .

Examples of the photosensitive resin include a photosensitive resin comprising a negative type diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition comprising an azide compound and a binder, and a cinnamic acid type photosensitive resin. Compositions and the like,
Among them, a photopolymerizable composition containing a photopolymerization initiator, a photopolymerizable monomer, and a binder as basic constituent elements is particularly preferable.

In the photosensitive layer, a portion irradiated with light becomes soluble and is removed by a developing process (hereinafter sometimes referred to as a "positive photosensitive resin layer"). Can also be used. As the photosensitive resin used for the positive photosensitive resin layer, a novolak-based resin can be mentioned, and it can be appropriately selected from known ones. For example, an alkali-soluble novolak resin described in JP-A-7-43899 can be suitably used. Further, as the positive photosensitive resin layer, for example, JP-A-6-148888
Patent Document 1: positive photosensitive resin layer, that is, a photosensitive resin comprising a mixture of an alkali-soluble resin described in the publication, 1,2-naphthoquinonediazidesulfonic acid ester as a sensitizer, and a thermosetting agent Layers can be suitably used. Further, the composition described in JP-A-5-262850 can also be used as a component of the positive photosensitive resin layer.

-Other Components- Examples of the polymerizable compound, polymerization initiator, surfactant, and adhesion aid include polymerizable compound B, polymerization initiator C, and polymerizable compound described in JP-A-11-133600. Surfactant,
Adhesion aids and the like can each be mentioned.

As described below, for forming a colored image such as a color filter, a coloring agent such as a dye or a pigment can be contained. As a coloring agent such as the dye or pigment, for example, Victoria Pure Blue B
O (CI. 42595), auramine (CI. 41)
000), Fat Black HB (CI. 2615)
0), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR
(CI Pigment Yellow 83), permanent
Carmine FBB (CI Pigment Red 14
6), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH
(CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fast Blue (CI Pigment Blue 15), Monolight First Black B
(CI Pigment Black 1), carbon black,

Further, C.I. I. Pigment Red 9
7, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 1
68, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I.
Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 15: 1, C.I.
I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22,
C. I. Pigment Blue 60, C.I. I. Pigment Blue 64 and the like.

The pigment must be uniformly dispersed in the photosensitive layer, and has a particle size of preferably 5 μm or less, particularly preferably 1 μm or less.

As the above-mentioned UV absorber, for example, UV absorbers of salicylate type, benzophenone type, benzotriazole type, cyanoacrylate type, nickel chelate type, hindered amine type and the like are preferably exemplified. Specific examples include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate, 2,4-di-hydroxy Benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy-5 '
-Methylphenyl) benzotriazole,

2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2 ' -Hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethol-4-pyridine)-
Sebacate, 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-
Tetramethylpiperidine condensate, bis-succinic acid (2,
2,6,6-tetramethyl-4-piperidenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-
Dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino)-
5-triazin-2-yl] amino} -3-phenylcoumarin and the like.

(Oxygen blocking film) On the photosensitive resin layer,
Further, it is preferable to form an oxygen barrier film and expose through the film. The oxygen barrier film preferably has low oxygen permeability and is preferably dispersed or dissolved in water or an aqueous alkaline solution, and may be appropriately selected from known materials. Among known oxygen barrier films, those formed by combining polyvinyl alcohol and polyvinylpyrrolidone are particularly preferable. For details, see JP-A-5-72724.
No., published in Japanese Unexamined Patent Publication No.

In this step, the photosensitive layer is formed on a substrate. As a method for forming the photosensitive layer on the substrate, a coating solution in which the above components are dissolved in a solvent is prepared, and a known coating solution is prepared. A method of applying a photosensitive layer on a temporary support by a known coating method by applying and drying a photosensitive layer on a substrate by a method, and providing a photosensitive layer on the substrate by transfer using a transfer material having a photosensitive layer applied and formed on a temporary support in advance by a known coating method Method and the like. In the case of the above method, the photosensitive layer can be peeled off from the temporary support and used as an independent sheet (photosensitive sheet).

The substrate is not particularly limited and can be appropriately selected according to the purpose. When the photosensitive layer is provided on the temporary support, the temporary support is not particularly limited and can be appropriately selected depending on the purpose. However, a flexible sheet is preferable.

Examples of the known coating method include a method using a spinner, a wiper, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder, and the like. After the application, the photosensitive layer or the photosensitive sheet can be obtained by drying.

As a specific embodiment of the transfer material in the above-mentioned method, it can be basically constituted in the same manner as a known photosensitive transfer material, and the simplest embodiment thereof is a temporary material made of a flexible plastic film or the like. This is a mode in which a thin layer (photosensitive layer, photosensitive resin layer) containing a photosensitive resin is formed on a support, and furthermore, the peelability at the interface between the support and the photosensitive layer is further reduced. An undercoat layer, an intermediate layer, a release layer, or the like, which can facilitate or impart cushioning properties, can be arbitrarily provided.

More specifically, a transfer material described in JP-A-4-208940, having a separation layer having a small adhesive force to a temporary support and a photosensitive resin layer, is disclosed in JP-A-5-173320.
Japanese Patent Application Publication No. JP-A-2003-133873, a photosensitive transfer material having a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer on a temporary support, and having the smallest adhesive force between the temporary support and the thermoplastic resin layer. Kaihei 5-
Japanese Patent Application Laid-Open No. 5-80503, which discloses a transfer material having a thermoplastic resin layer, a separation layer and a photosensitive resin layer and having the smallest adhesive force between the thermoplastic resin layer and the separation layer.
JP-A No. 6-1980, having a thermoplastic resin layer, an intermediate layer and a photosensitive resin layer on a temporary support, a photosensitive transfer material having the smallest adhesive force between the temporary support and the thermoplastic resin layer, And the like. Among them, an integral transfer material such as a photosensitive transfer material described in JP-A-5-72724 is preferable. As a specific example, an alkali-soluble thermoplastic resin layer on a temporary support, A photosensitive transfer material in which an oxygen barrier layer (intermediate layer), a photosensitive layer, and a protective film are laminated in this order is preferred. For details of the thermoplastic resin layer, the description of each of the above-mentioned publications can be referred to.

When a photosensitive layer is provided on a substrate by the above-described method, first, if necessary, the protective film of the transfer material is removed, and the photosensitive layer is bonded to the substrate under pressure and heat. This can be performed by peeling the temporary support from the substrate. A known laminator and vacuum laminator can be used for lamination, and an auto-cut laminator can be used to further improve productivity.

[Exposure Step] In the exposure step, the photosensitive layer provided on the substrate is subjected to imagewise pattern exposure. Pattern exposure means irradiating the photosensitive layer with patterned light through a shadow mask on which an image pattern is formed. In some cases, light irradiation may be performed without using a shadow mask. As a light source used for light irradiation, a known light source such as an ultra-high pressure mercury lamp or a xenon lamp can be used. The photomask can be appropriately selected from known ones.

[Image Forming Step] In the pixel forming step, an unnecessary photosensitive resin layer (a photosensitive layer in an unnecessary area not involved in pixel formation) and the like are removed by a developing process to form an image on a substrate. As the developing solution used for the developing treatment, the developing solution of the present invention described above is used.

The developing solution can be used as a bath solution or a spray solution. Examples of the developing method include paddle development, shower development, shower & spin development, and dip development. Among them, shower development using the same developer for multiple substrates,
Shower & spin development, dip development and the like are preferred. When removing the uncured part (unnecessary area) of the photosensitive resin layer,
Methods such as rubbing with a rotating brush or a wet sponge in a developer can be combined. Usually, the temperature of the developer is preferably from 20 to 40C. After development processing, distilled water,
It is also preferable to include a washing step with ion-exchanged water, ultrapure water, or the like.

As described above, by using the developing solution of the present invention as described above, a stable developing process is realized, and a high-definition image can be stably formed.

<Method for Producing a Color Filter> The method for producing a color filter of the present invention comprises the same steps as the image forming method of the present invention, that is, a photosensitive layer forming step, an exposing step, and an image forming step. At least, the developer of the present invention described above is used as the developer used in the developing step. Further, in the photosensitive layer forming step, a coloring agent is further contained in the photosensitive layer formed on the substrate, and in the image forming step, a colored image is formed on the substrate.

As the coloring agent, the same coloring agents as those usable in the image forming method of the present invention, such as dyes and pigments, can be used. Further, the thickness of the color filter is preferably 1 to 7 μm, more preferably 1 to 5 μm.

Next, an example of manufacturing a color filter will be described. The color filter has three processes (a photosensitive layer forming process, a photosensitive layer forming process, a red (R), a green (G), a blue (B)) pixel, and a black (K) black matrix.
Exposure step and image forming step) are repeatedly performed in order. For example, the following steps (1) to (4) can be performed by RG
The repetition may be performed for each pixel of B.

(1) At least a photosensitive resin is added to a solvent to form a coating liquid, and a coating liquid (a coating liquid for a photosensitive layer) in which a pigment is dispersed is further applied and dried, or as described above. Using a transfer material having a photosensitive layer formed on a temporary support in advance and transferring the same to provide a colored photosensitive layer on a substrate (photosensitive layer forming step); A thermoplastic resin layer and an intermediate layer may be formed between the substrate and the photosensitive layer. (2) a step of exposing the colored photosensitive layer in a pattern through a photomask (exposure step); (3) after the exposure, if necessary, developing and removing the thermoplastic resin layer and the intermediate layer; and Developing the photosensitive layer to form pixels on the substrate along the exposed area of the photosensitive layer on the substrate (image forming step); after the above (3), heating the pixels formed on the substrate by heat treatment It is also possible to provide a step of baking and further curing (heat treatment step).

In the above step (1), a pigment having a desired hue is selected as a pigment, and a coating liquid for each of red (R), green (G), blue (B) and black (K) is prepared and used. Then, RGB pixels and a black matrix are formed between the pixels in order on the substrate. After the second color, the layer may be formed so as to cover the pixels of the first color, and only the uncured area is dissolved and removed by the developing treatment. The black matrix may be formed before or after formation of RGB pixels.

The above steps (1) to (3) are general methods in an image forming method for forming an image using a photosensitive transfer material, and are described, for example, in JP-A-5-173320. . As a typical image forming method, a photosensitive resin composition layer of a photosensitive transfer material is overlaid on the surface of a transparent substrate to be installed on a liquid crystal display element, and after removing the support,
A step of exposing the photosensitive resin composition layer on the material to be transferred to the photosensitive resin composition layer via a photomask, a step of heating the photosensitive resin composition layer after the exposure, and a developing treatment to dissolve and remove unexposed portions. A method combining steps and the like can be used.

The substrate for producing the color filter can be appropriately selected according to the purpose, but a known glass plate, a soda glass plate having a silicon oxide film formed on the surface, and the like are preferable.

As described above, a decrease in developability due to a decrease in pH during development is small, and a high-resolution color filter can be formed stably.

<Method of Manufacturing Active Matrix Substrate with Color Filter> The method of manufacturing an active matrix substrate with a color filter according to the present invention comprises a method of forming a photosensitive layer containing at least a photosensitive resin which can be alkali-developed and a coloring agent on the active matrix substrate. (A photosensitive layer forming step) and a step of imagewise patternwise exposing the photosensitive layer on the active matrix substrate (exposure step)
And a step of forming a colored image on the substrate by a developing process (image forming process), wherein the developing solution of the present invention is used in the developing process in the image forming process. If necessary, other steps such as a black matrix forming step may be included.

In the photosensitive layer forming step in the present manufacturing method, a photosensitive layer containing at least a photosensitive resin capable of being alkali-developable and a coloring agent is formed on an active matrix substrate. The details of the photosensitive resin, the colorant, and the photosensitive layer are as described above in the image forming method of the present invention.

As a substrate, an active matrix substrate is used, and a colored image of a pattern serving as a color filter is directly formed on the substrate. By forming a color filter on an active matrix substrate, unlike the conventional method, the drive-side substrate and the color filter-side substrate manufactured in different processes can be integrally manufactured without combining them. An active matrix substrate with a high-definition color filter without displacement can be formed. In addition, it contributes to the realization of cost reduction.

The active matrix substrate refers to a pixel electrode (an image displayable element) in which an active element such as a thin film transistor (TFT), a single crystal silicon transistor (MOSFET), or a diode is joined to a light transmitting substrate. (An electrode for controlling the liquid crystal material of the pixel portion). From the viewpoint of functioning as a color filter, for example, a light-transmissive material such as glass or plastic is preferably used as the substrate.

In the present invention, the black matrix forming step may be provided, and a black matrix may be formed between pixels. The black matrix is required to have both functions of light blocking and light reflection,
It can be formed in the same manner as the photosensitive layer using a black colorant. Among them, an embodiment using a photosensitive transfer material corresponding to the above method is preferable.

As described above, a colored image (color filter) can be formed directly on the active matrix substrate without adversely affecting the semiconductor characteristics of the TFT elements and the like on the substrate, thereby realizing cost reduction. be able to. In addition, a decrease in developability due to a decrease in pH during development is small, and a high-resolution colored image can be stably formed.

<Liquid Crystal Display Element> The liquid crystal display element of the present invention comprises at least an active matrix substrate with a color filter obtained by the method of manufacturing an active matrix substrate with a color filter of the present invention, and an active matrix substrate with the color filter. And a liquid crystal material sealed between the color filter active matrix substrate and the counter substrate, and, if necessary, an alignment film, a black matrix layer, and the like. Can also be provided.

The alignment film has a function of defining the alignment direction of the liquid crystal compound in the liquid crystal phase, and can be formed of a polymer such as polyimide, polyvinyl alcohol, or gelatin. Is preferably subjected to an orientation treatment such as a rubbing treatment. Further, the alignment film can be provided on a surface of each of the active matrix substrate with a color filter and the opposing substrate which is in contact with the liquid crystal material. Further, the black matrix layer can be formed in the same manner as described above.

The opposing substrate has at least an electrode layer on a light-transmitting substrate and, if necessary, other layers such as a black matrix layer and an alignment film. The electrode layer can be formed using a material such as a metal or a metal oxide such as ITO. The same applies to the black matrix layer and the alignment film.

The configuration of the liquid crystal display element is slightly different depending on the above-mentioned aspect of the active matrix substrate with a color filter of the present invention. The active matrix substrate with a color filter and the opposing substrate are fixed by forming a predetermined space via a spacer such as a resin ball, for example. The liquid crystal material of the present invention is sealed by injecting a liquid crystal material into the space. An element can be manufactured.
The liquid crystal material can be appropriately selected from known materials according to the purpose.

As described above, by providing the active matrix substrate with a color filter of the present invention, a high-resolution liquid crystal display device having excellent pattern accuracy can be manufactured at lower cost.

[0072]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
“Parts” and “%” in the examples all represent “parts by weight” and “% by weight”. (1) Preparation of Color Filter All samples in this example were prepared under yellow light. (Example 1) <Preparation of photosensitive transfer material> A polyethylene terephthalate film temporary support having a thickness of 75 µm (conductive fine particles on the side opposite to the coated surface (see paragraph [0046] of JP-A-5-173320). 0.18 μm for conductive sample (9))
Is prepared by applying a coating liquid for a thermoplastic resin layer having the following formulation H1 onto the temporary support while transporting the temporary support, and drying. After sequentially passing through the zones and drying, a coating solution for an oxygen barrier film having the following formulation B1 was further applied on the layer with a geser, and dried successively through a drying zone at a temperature of 50 to 120 ° C. In this way, four temporary supports in which the thermoplastic resin layer and the oxygen barrier film were laminated in this order were produced.

[Thermoplastic resin layer formulation H1] Vinyl chloride / vinyl acetate copolymer: 290.0 parts (weight ratio: polyvinyl chloride / vinyl acetate = 75/25, degree of polymerization: about 400, MPR-TSL, Nissin Chemical Co., Ltd.)-Vinyl chloride-vinyl acetate-maleic acid copolymer: 76.0 parts (weight ratio: vinyl chloride / vinyl acetate / maleic acid = 86/13/1, degree of polymerization: about 400 , MPR-TM, manufactured by Nissin Chemical Co., Ltd.)-Dibutyl phthalate: 88.5 parts-Fluorine surfactant: 5.4 parts (F-177P, manufactured by Dainippon Ink Co., Ltd.)・ MEK: 975.0 copies

[Oxygen barrier film formulation B1]-Polyvinyl alcohol ... 173.2 parts (PVA205, saponification rate = 80%, manufactured by Kuraray Co., Ltd.)-Fluorine surfactant ... 8 parts-Distilled water- ..2800 copies

Next, a compound having the following composition was mixed to prepare coating solutions K1, R1, G1 and B1 for the photosensitive resin layer, and each of the four temporary supports obtained above was coated on each oxygen barrier film. A coating liquid K1, R1, G1, or B1 for a photosensitive resin layer is applied and dried by sequentially passing through a drying zone. On a temporary support, a thermoplastic resin layer having a dry film thickness of 14.6 μm,
A 1.6 μm dry film oxygen barrier film, and a 2 μm dry film photosensitive resin layer (black (K), red (R), green (G) or blue
(B)) was formed by laminating in this order, and a protective film (a polypropylene film having a thickness of 12 μm) was further pressure-bonded with a nip roller to form a protective film on the photosensitive resin layer, and then wound up. . As above,
Photosensitivity in which a thermoplastic resin layer, an oxygen barrier film, a photosensitive resin layer (black (K), red (R), green (G) or blue (B)) and a protective film are laminated on a temporary support. A transfer material was prepared. For each photosensitive transfer material, using the symbol (K1, R1, G1, B1) of the coating solution for the photosensitive resin layer used,
A black (K) photosensitive transfer material K1, a red (R) photosensitive transfer material R1, and a green (G) photosensitive transfer material G, respectively.
1, or blue (B) photosensitive transfer material B1.

[Composition of Photosensitive Resin Layer Coating Solution K1] Benzyl methacrylate / methacrylic acid copolymer: 60 parts (copolymer molar ratio = 73/27, molecular weight: 30,000) Pentaerythritol tetraacrylate 43.2 parts ・ Michler's ketone ・ ・ ・ 2.4 parts ・ 2- (o-chlorophenyl) -4,5-di ・ ・ ・ 2.5 parts Phenylamidazyl dimer ・ Carbon black ・ ・ ・ 5.6 parts・ Methyl cellosolve acetate ・ ・ ・ 560 parts ・ Methyl ethyl ketone ・ ・ ・ 280 parts

[Composition of Photosensitive Resin Layer Coating Solution R1] Benzyl methacrylate / methacrylic acid copolymer: 60 parts (copolymer molar ratio = 73/27, molecular weight: 30,000) Pentaerythritol tetraacrylate 43.2 parts-Michler's ketone ... 2.4 parts-2- (o-chlorophenyl) -4,5-di ... 2.5 parts Phenylamidazir dimer-Irgasin red BPT (red)-・ 5.4 parts ・ Methyl cellosolve acetate ・ ・ ・ 560 parts ・ Methyl ethyl ketone ・ ・ ・ 280 parts

[Composition of Photosensitive Resin Layer Coating Solution G1] Benzyl methacrylate / methacrylic acid copolymer: 60 parts (copolymerization molar ratio = 73/27, molecular weight: 30,000) Pentaerythritol tetraacrylate 43.2 parts-Michler's ketone ... 2.4 parts-2- (o-chlorophenyl) -4,5-di ... 2.5 parts Phenylamidazyl dimer-Copper phthalocyanine (green) ... 5 .6 parts ・ Methyl cellosolve acetate ・ ・ ・ 560 parts ・ Methyl ethyl ketone ・ ・ ・ 280 parts

[Composition of Photosensitive Resin Layer Coating Solution B1] Benzyl methacrylate / methacrylic acid copolymer: 60 parts (copolymerization molar ratio = 73/27, molecular weight: 30,000) Pentaerythritol tetraacrylate 43.2 parts ・ Michler's ketone ・ ・ ・ 2.4 parts ・ 2- (o-chlorophenyl) -4,5-di ・ ・ ・ 2.5 parts Phenylamidazyl dimer ・ Sudan blue (blue) ・ ・ ・ 5 .4 parts ・ Methyl cellosolve acetate ・ ・ ・ 560 parts ・ Methyl ethyl ketone ・ ・ ・ 280 parts

<Production of Active Matrix Substrate> Gate signal lines and additional capacitance electrodes were formed on an array substrate, and a gate insulating film was formed thereon. Thereafter, a semiconductor layer and a channel protective layer were formed in this order on the gate insulating film, and further, an n + Si layer serving as a source and a drain of a thin film transistor (TFT) was formed. Then, a metal layer and an ITO film were formed by a sputtering method, and these were patterned to form a drain signal line and a source signal line. In this way, TF is placed on the substrate.
An active matrix substrate provided with T was produced.

<Formation of Colored Image (Color Filter)> On the surface of the active matrix substrate obtained as described above on which the TFT is provided, after removing the protective film from the photosensitive transfer material K1, the photosensitive resin layer Were laminated so as to be in contact with each other, and were laminated at a temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.0 m / min. Next, after pattern exposure with an irradiation energy of 20 mJ / cm ² using an ultra-high pressure mercury lamp, shower development was performed with a developer P1 having the following composition (shower developing machine having a tank capacity of 25 liters;
For 35 seconds), the thermoplastic resin layer and the oxygen barrier film were removed. [Composition of developer P1]-Ultrapure water: 97 parts-Triethanolamine: 3 parts (Alkali metal ion concentration: 50 ppb)

Subsequently, shower development was carried out using a developer C1 for developing a photosensitive resin of the present invention having the following composition (tank capacity 25
(Liter shower developing machine; 33 ° C., 26 seconds), the uncured portion of the photosensitive resin layer was developed and removed, and a black image patterned imagewise was formed. [Composition of developer C1 for developing photosensitive resin] In 98 parts of pure water, monoethanolamine (pKa9.
5) 1.22 parts and a nonionic surfactant (Pluronic, manufactured by Asahi Denka Kogyo KK) were added to make a uniform solution (0.2 mol / l). Carbon dioxide gas was blown into the liquid, and the pH was adjusted to 9.5 with a pH meter (manufactured by Toa Denpa Kogyo KK) (alkaline metal ion concentration: 50 ppb).

Thereafter, post-exposure was performed from both sides of the substrate on which the black image was formed with irradiation energy of 500 mJ / cm ² , followed by post-baking at 220 ° C. for 25 minutes to form black pixels.

Further, using the photosensitive transfer materials R1, G1, and B1 sequentially, the same operation as described above was repeated, and red, green,
The active matrix substrate C1 with a color filter of the present invention (depending on the developer used for developing the photosensitive resin layer) formed of blue pixels and composed of black, red, green, and blue colored images (pixels) is formed. Produced. These steps are
One day was provided for each color pixel formation, and it took four days in total.

<Preparation of Liquid Crystal Display Element> An alignment film was formed on the colored image of the active matrix substrate C1 with a color filter obtained as described above, and the surface of the alignment film was subjected to a rubbing treatment. On the other hand, a counter electrode and an alignment film were laminated on a counter substrate in this order. The alignment film on the active matrix substrate C1 with a color filter and the alignment film on the counter substrate are arranged so as to face each other, and a gap is provided between the two alignment films via a spacer, and the alignment film is fixed. Inject the material,
A liquid crystal display device of the present invention was produced.

(Examples 2 to 7) In the preparation of the developer C1 for developing a photosensitive resin in Example 1, the pH was adjusted by adding an acid agent (see Table 1) instead of adjusting the pH by blowing carbon dioxide gas (see Table 1). pH value: see Table 1), except that the photosensitive resin developing solutions C2 to C of the present invention were prepared in the same manner as the photosensitive resin developing solution C1 of Example 1 with the compositions shown in Table 1 below.
7 was prepared. The alkali metal ion concentration of each developer for developing a photosensitive resin obtained above was 0.1 ppm for C2 and 0.1 ppm for C2.
3:80 ppb, C4: 90 ppb, C5: 60 pp
b, C6: 50 ppb, C7: 80 ppb. The color filter of the present invention was prepared in the same manner as in Example 1 except that the photosensitive resin developing developers C2 to C7 were used instead of the photosensitive resin developing developer C1 used in Example 1. Active matrix substrates C2 to C7 were prepared. Further, a liquid crystal display device of the present invention was produced in the same manner as in Example 1 using the active matrix substrates with color filters C2 to C7.

(Comparative Example 1) The developer C1 of the photosensitive resin developing solution of Example 1 was prepared in the same manner as in Example 1 except that the pH was not adjusted by blowing carbon dioxide gas. Comparative developer c8 was prepared in the same manner as described above (pH 11.2, alkali metal ion concentration: 95 p.
pb). Further, an active matrix substrate c8 with a color filter was prepared in the same manner as in Example 1, except that the comparative developer c8 was used instead of the photosensitive resin developing developer C1 used in Example 1. A liquid crystal display device was manufactured in the same manner as in Example 1 using the active matrix substrate c8 with a color filter.

Comparative Example 2 In the preparation of the developer C1 for developing a photosensitive resin in Example 1, the concentration of monoethanolamine was 0.15 mol / l, and the pH was not adjusted by blowing carbon dioxide gas. Other than the above, the comparative developer c9 was the same as the photosensitive resin developing developer C1 of Example 1.
(PH 9.5, alkali metal ion concentration: 7)
0 ppb). Further, an active matrix substrate c9 with a color filter was prepared in the same manner as in Example 1, except that the comparative developer c9 was used in place of the photosensitive resin developing developer C1 used in Example 1. A liquid crystal display device was manufactured in the same manner as in Example 1 using the active matrix substrate c9 with a color filter.

[0089]

[Table 1]

(Examples 8 to 14) In the preparation of the developing solutions C1 to C7 for the photosensitive resin in Examples 1 to 7, monoethanolamine was replaced with N, N-dimethylaminoethanol (p
Ka9.7) instead of the composition shown in Table 2 below.
In the same manner as the photosensitive resin developing developers C1 to C7 of Examples 1 to 7, respectively, the photosensitive resin developing developer C of the present invention was used.
10-C16 were prepared. The alkali metal ion concentration of each developer for developing a photosensitive resin obtained above was C10: 80.
ppb, C11: 90 ppb, C12: 100 ppb,
C13: 70 ppb, C14: 60 ppb, C15: 5
0 ppb and C16: 90 ppb. Further, in the same manner as in Example 1 except that the photosensitive resin developing developers C10 to C16 were used in place of the photosensitive resin developing developers C1 to C7 used in Examples 1 to 7, Active matrix substrates with color filters C10 to C16 of the invention
And using the active matrix substrates with color filters C10 to C16 in the same manner as in Example 1,
A liquid crystal display device of the present invention was produced.

(Comparative Example 3) The developer C10 for photosensitive resin development of Example 8 was prepared, except that the pH was not adjusted by blowing carbon dioxide gas in the preparation of the developer C10 for developing photosensitive resin in Example 8. Comparative developer c17
(PH 12, alkali metal ion concentration: 70)
ppb). Further, an active matrix substrate c17 with a color filter was produced in the same manner as in Example 8, except that the comparative developer c17 was used instead of the photosensitive resin developing developer C10 used in Example 8. A liquid crystal display device was produced in the same manner as in Example 8 using the active matrix substrate with color filter c17.

Comparative Example 4 In the preparation of the developer C10 for developing a photosensitive resin in Example 8, the concentration of N, N-dimethylaminoethanol was 0.13 mol / l, and the pH was adjusted by blowing carbon dioxide gas. A comparative developer c17 was prepared (pH 9.7, alkali metal ion concentration: 80 ppb) in the same manner as in the photosensitive resin developing developer C10 of Example 8, except that this was not performed. Further, an active matrix substrate c17 with a color filter was produced in the same manner as in Example 8, except that the comparative developer c17 was used instead of the photosensitive resin developing developer C10 used in Example 8. A liquid crystal display device was produced in the same manner as in Example 8 using the active matrix substrate with color filter c17.

[0093]

[Table 2]

(Examples 15 to 21) In the preparation of the developing solutions C1 to C7 for the photosensitive resin in Examples 1 to 7, monoethanolamine was replaced with N-methylaminoethanol (pKa).
10) In place of the compositions shown in Table 3 below, in the same manner as the photosensitive resin developing developers C1 to C7 of Examples 1 to 7, respectively, the photosensitive resin developing developers C19 to C19 to
C25 was prepared. The alkali metal ion concentration of each photosensitive resin developing solution obtained above was C19: 90 pp.
b, C20: 70 ppb, C21: 80 ppb, C2
2:90 ppb, C23: 100 ppb, C24: 60
ppb, C25: 50 ppb. Example 1
In the same manner as in Example 1 except that the photosensitive resin developing developers C19 to C25 were used in place of the photosensitive resin developing developers C1 to C7 used in Examples 1 to 7, the color filter with the color filter of the present invention was used. Active matrix substrates C19 to C25 were prepared, and a liquid crystal display device of the present invention was prepared in the same manner as in Example 1 using the active matrix substrates C19 to C25 with color filters.

(Comparative Example 5) The developer C19 of Example 15 was prepared except that the pH was not adjusted by blowing carbon dioxide gas in the preparation of the developer C19 for developing photosensitive resin in Example 15. Comparative developer c in the same manner as
No. 26 was prepared (pH 12.3, alkali metal ion concentration: 80 ppb). Further, instead of the developer C19 for developing a photosensitive resin used in Example 15, the comparative developer c26 was used.
An active matrix substrate c26 with a color filter was produced in the same manner as in Example 15 except that was used, and a liquid crystal display device was produced in the same manner as in Example 15 using the active matrix substrate c26 with a color filter.

Comparative Example 6 In the preparation of the developer C19 for developing a photosensitive resin in Example 15, the concentration of N-methylaminoethanol was 0.11 mol / l, and the pH was not adjusted by blowing carbon dioxide gas. Except for this, a comparative developer c27 was prepared in the same manner as the photosensitive resin developing developer C19 of Example 15 (pH 10, alkali metal ion concentration: 70 ppb). Further, an active matrix substrate c27 with a color filter was prepared in the same manner as in Example 15, except that the comparative developer c27 was used in place of the photosensitive resin developing developer C19 used in Example 15. A liquid crystal display device was manufactured in the same manner as in Example 15 using the active matrix substrate c27 with a color filter.

[0097]

[Table 3]

(Comparative Examples 7 to 9) The developer C2 for developing a photosensitive resin prepared in Example 2 was further added with sodium ions (Na
⁺ ) And the Na ⁺ content is 0.2 ppm, 0.5 pp
m and 1 ppm of comparative developer solutions c28, c29 and c30 were prepared. Further, instead of the photosensitive resin developing solution C2 used in Example 2, the comparative developing solutions c28, c29 and c3 were used.
Active matrix substrates c28, c29, c with color filters in the same manner as in Example 2 except that 0 was used.
30 were produced.

(Comparative Example 10) The monoethanolamine (0.2 mol / l) used in the preparation of the developer C1 for developing a photosensitive resin in Example 1 was replaced with sodium carbonate (0.024).
A comparative developer c31 was prepared in the same manner as in Example 1 except that the M solution was used. Further, an active matrix substrate c31 with a color filter was prepared in the same manner as in Example 1, except that the photosensitive resin developing developer c31 was used instead of the photosensitive resin developing developer C1 used in Example 1. Produced. The sodium ion (Na ⁺ ) concentration in the developer C31 was 0.5%.

(Evaluation)-Stability with time-As described above, using the developing solution obtained in each of the examples, a photosensitive developer performed by a shower developing machine having a tank capacity of 25 liters (liquid temperature: 33 ° C., developing time: 26 seconds). In the developing process of the conductive resin layer, the inside of the shower developing machine was set to an outside air inflow coefficient 11 and as shown in Table 4 below, each developing solution was allowed to flow in the machine for a predetermined time (0, 0.5, 1, 2, 2, 3) before the developing process. 3,4,6,8,10 hours
(h)) After circulating and stirring, the photosensitive resin layer was subjected to development processing (liquid temperature 33 ° C., development time 26 seconds). The developer for developing a photosensitive resin of the present invention (C1 to C7, C10 to c16,
C19 to C25) and comparative developers (c8, c9, c1)
7, c18, c26, and c27), the time until development was completed was measured, and this was used as an index indicating the stability over time of each developer. The evaluation results are shown in Table 4 below,
The values in the table indicate the time (seconds) required to complete the development.

-Defective rate-The operation test of the TFT was performed on the active matrix substrates C1 and C2 with color filters of the present invention and the active matrix substrates c28 and c31 with color filters of the comparative examples obtained above, and the normal operation was performed. The defective rate was determined as ○ for those that did not work and × (NG) for those that did not work properly. The evaluation results are shown in Table 5 below.

[0102]

[Table 4]

[0103]

[Table 5]

From the results in Table 4 above, it was found that (pKa-0.5 of amine compound) ≦ pH by using an acid agent such as carbon dioxide or acid.
The developer (C) for developing a photosensitive resin according to the present invention, wherein the pH of the developer is adjusted to a range of ≦ (pKa of amine compound + 1.2).
1 to C7, C10 to C16, and C19 to C25), there was almost no decrease in developability even when circulated in the developing machine for a long time. Further, no influence by the type of acid was observed. On the other hand, the comparative developers (c8, c17, c26) prepared without adjusting the pH had too high a pH value and too high developability to stably form a high-resolution colored image. The comparative developer (c9, c18, c27) in which the concentration of the developing agent in the developer was reduced and the pH value was adjusted to the range specified in the present invention could form a relatively high-resolution colored image. However, the stability of the developing solution was lacking, and sufficient developing performance could not be secured.

From the results shown in Table 5, the active matrix substrate C1 with a color filter and the active matrix substrate C1 with a color filter produced using the developer (C1 to C2) for developing a photosensitive resin of the present invention having an alkali metal ion concentration of 0.1 ppm or less were obtained. In C2,
A high-definition, high-resolution colored image (color filter) can be formed stably, and the failure rate (malfunction or operation) does not affect the operation characteristics of TFT elements on the substrate (malfunction or malfunction). And the ratio of no).
Incidentally, the developer for developing the photosensitive resin of the present invention (C3 to C7, C
10 to C16, C19 to C25), the same results were obtained. On the other hand, 0.1 pp
m containing a comparison developer (c2
8 to c31), the active matrix substrates with color filters c18 to c23 manufactured using
The influence on the operation characteristics of the FT element was recognized, and the defect rate was high.

The active matrix substrates with color filters of the present invention (C1 to C7, C10 to C16, C1
9 to C25) were excellent in pattern accuracy and high in resolution, and could be stably manufactured at low cost. Active matrix substrates with color filters of comparative examples (c8, c9, c17, c18, c26, c
The liquid crystal display device manufactured using the method 27) was inferior in resolution.

[0107]

According to the present invention, it is possible to provide a developing solution which does not adversely affect the semiconductor characteristics of a TFT element or the like and which can stably form a high-definition image pattern and has excellent stability over time. According to the present invention, it is possible to provide an image forming method capable of stably forming a high-definition image without a decrease in developability due to a change in pH during a developing process. In addition, it is possible to provide a method of manufacturing a color filter that can stably form a high-resolution colored image (color filter) without a decrease in developability due to a change in pH during a development process. Further, according to the present invention, there is provided a method of manufacturing an active matrix substrate with a color filter capable of stably forming a high-resolution colored image on an active matrix substrate without considering adverse effects on semiconductor characteristics such as TFT elements. Can be provided. According to the present invention, a high-resolution liquid crystal display element having excellent pattern accuracy can be provided at low cost.

Claims (8)

[Claims] 1. A developer for developing a photosensitive resin containing an amine compound as a developing agent, wherein the pH value is in the range of (pKa of amine compound-0.5) ≦ pH ≦ (pKa of amine compound + 1.2). A developer for developing a photosensitive resin, characterized in that the developer is adjusted to: 2. The developer for developing a photosensitive resin according to claim 1, wherein the pH value is adjusted by adding at least one selected from a mineral acid, an organic acid, carbon dioxide, and an aqueous solution of carbon dioxide. 3. The developer for developing a photosensitive resin according to claim 1, wherein the pH value is adjusted by blowing carbon dioxide gas. 4. An alkali metal ion concentration of 0.1 pp
The developer for developing a photosensitive resin according to any one of claims 1 to 3, which is not more than m. 5. A step of forming a photosensitive layer containing a photosensitive resin capable of being alkali-developed on a substrate, a step of patternwise exposing the photosensitive layer on the substrate in an imagewise manner, and an image on the substrate by a developing process. Forming a developer, wherein the developer used in the developing process is the developer for developing a photosensitive resin according to any one of claims 1 to 4. Characteristic image forming method. 6. A step of forming a photosensitive layer containing a photosensitive resin capable of being alkali-developable on a substrate, a step of imagewise pattern-exposing the photosensitive layer on the substrate, and a developing process to form an image on the substrate. A process for forming a color filter, wherein the developer used for the development process is the developer for developing a photosensitive resin according to any one of claims 1 to 4, And a method for producing a color filter, wherein the photosensitive layer further contains a colorant to form a colored image on a substrate. 7. A step of forming, on an active matrix substrate, a photosensitive layer containing at least a photosensitive resin capable of developing with an alkali and a colorant, and patternwise exposing the photosensitive layer on the active matrix substrate to an image. 5. A developing solution for developing a photosensitive resin according to claim 1, wherein the developing solution comprises at least a step of forming a colored image on a substrate by a developing process, and the developing solution used in the developing process is a developing solution for developing a photosensitive resin according to claim 1. A method for manufacturing an active matrix substrate with a color filter, characterized by comprising: 8. An active matrix substrate with a color filter obtained by at least the method for manufacturing an active matrix substrate with a color filter according to claim 7, and a light transmissive member arranged to face the active matrix substrate with a color filter. And a liquid crystal material sealed between the color filter active matrix substrate and the counter substrate.