JP2003337430A - Developer, colored image forming method, method for producing color filter and method for producing color filter affixed array substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer excellent in residue removing property and capable of forming a colored image having good contact resistance. <P>SOLUTION: The developer contains a nitrogen compound containing two or more nitrogen atoms in one molecule, a compound having an aromatic ring and a carbonate. Preferably the nitrogen compound containing two or more nitrogen atoms in one molecule is at least one selected from triethylenetetramine, pentaethylenehexamine and di-tert-butylethylenediamine, the aromatic ring is at least one of naphthalene and benzene rings and the carbonate contains no metal ion. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a developing solution, a method for forming a colored image using the same, a method for producing a color filter, and a method for producing an array substrate with a color filter.

[0002]

2. Description of the Related Art In recent years, color filters have been widely used in liquid crystal display devices, sensors, color separation devices and the like. As a method of manufacturing this color filter,
Conventionally, a method has been adopted in which a dyeable resin, for example, natural gelatin or casein is patterned and dyed there mainly with a dye to obtain pixels. However, the pixel obtained by this method has a problem that the heat resistance and the light resistance are low due to restrictions of the material.

Therefore, recently, a method of using a photosensitive material in which a pigment is dispersed for the purpose of improving heat resistance and light resistance has attracted attention, and many studies have been conducted. It is known that according to this method, the manufacturing method is simplified and the color filter obtained is stable and has a long life. The production of a colored image using a photoresist in which a pigment is dispersed in this manner has been praised for the stability of the obtained image and the long life.

However, even in the above method, it is difficult to develop a photoresist in which a pigment is dispersed, and it is difficult to satisfy all the problems of developing time, resolution and development residue. In particular, when a metal ion-free developing solution used for forming a color filter on an array substrate is used, there is a problem that the contact resistance decreases due to the residue.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the various problems in the prior art and achieve the following objects. That is, the present invention provides a developer capable of forming a colored image having excellent residue removability and good contact resistance even when containing no metal ion, a colored image forming method using the developer, and a color filter. And a manufacturing method of
It is an object to provide a method for manufacturing an array substrate with a color filter.

[0006]

Means for solving the above-mentioned problems are as follows. That is, <1> A developing solution containing a nitrogen compound containing two or more nitrogen atoms in the molecule, a compound having an aromatic ring, and a carbonate. <2> The developer according to <1>, wherein the nitrogen compound containing two or more nitrogen atoms in the molecule is at least one of triethylenetetramine, pentaethylenehexamine, and di-tert-butylethylenediamine. is there. <3> The developer according to <1> or <2>, wherein the aromatic ring is at least one of a naphthalene ring and a benzene ring. <4> The carbonate is the developer according to any one of <1> to <3>, which does not contain a metal ion. <5> The developing solution according to any one of <1> to <4>, wherein the content of the compound having an aromatic ring in the developing solution is 0.1 to 50% by mass. <6> The developer according to any one of <1> to <5>, wherein the content of the nitrogen compound containing two or more nitrogen atoms in the molecule is 0.1 to 50% by mass. is there. <7> The content of carbonate in the developer is 0.1 to 5
The developing solution according to any one of <1> to <6>, which is 0% by mass. <8> At least in the method for forming a colored image in which a alkali-developable photosensitive resin layer is formed on a substrate, exposed and developed to form a colored image, the development is performed by any one of the above <1> to <7>. The method for forming a colored image is characterized in that it is carried out using the developing solution described in 1. <9> The photosensitive resin layer is a resin having an acid value of 20 to 300,
The method for forming a colored image according to <8> above, which is formed by a colored image forming material containing a pigment, a monomer containing at least one photopolymerizable unsaturated bond in the molecule, and a photopolymerization initiator. <10> A method for producing a color filter, in which at least a photosensitive resin layer capable of alkali development is formed on a substrate, exposed and developed to form a plurality of colored images on the same substrate, wherein the development includes A method for producing a color filter, which is performed using the developer according to any one of <1> to <7>. <11> A method for producing an array substrate with a color filter in which at least a photosensitive resin layer capable of alkali development is formed on a TFT array substrate, exposed and developed to form a plurality of colored images on the same TFT array substrate. Therefore, in the method for producing an array substrate with a color filter, the development is performed using the developing solution according to any one of <1> to <7>.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Developer] The developer of the present invention is an alkaline developer, which contains a predetermined nitrogen compound, a compound having an aromatic ring, and a carbonate, and optionally other components. In the developer of the present invention, the nitrogen compound has a role of effectively blocking the acidic group (carboxyl group etc.) in the resin forming the photosensitive layer from being gradually dissolved by the base when the photosensitive layer is developed. Have. Further, the carbonate contained in the developer of the present invention has a role of entering the photosensitive layer during development of the photosensitive layer and effectively swelling the photosensitive layer. Furthermore, the compound having an aromatic ring contained in the developer of the present invention has a role of peeling the swollen photosensitive layer. Therefore, according to the developer of the present invention, in the portion of the photosensitive layer to be removed, the photosensitive layer is abruptly peeled as minute pieces by the swelling action of the carbonate while suppressing the gradual dissolution of the photosensitive layer. (Hereinafter, it may be referred to as “fine piece peeling”.) As a result, it is possible to efficiently form an image with excellent residue removability and good contact resistance.

-Nitrogen Compound- The number of nitrogen atoms in the nitrogen compound must be 2 or more in the molecule, and is preferably 3 or more. When the number of nitrogen atoms is less than 2 in the molecule, it is not possible to effectively prevent the resin of the photosensitive layer from gradually dissolving. Therefore,
Since the photosensitive layer cannot be peeled off into minute pieces and the photosensitive layer is gradually dissolved during development, the residue removability after development is poor.

The nitrogen compound is not particularly limited as long as it contains two or more nitrogen atoms in the molecule, but for example, di-tertbutylethylenediamine, triethylenetetramine, pentaethylenehexamine, tetramethyldiaminohexane, Examples thereof include tetrabutyldiethylenetriamine, hexamethylenetetramine, pentakis (2-hydroxypropyl) diethylenetriamine, pentamethyldiethylenetriamine, and 2 (2- (2-dimethylamino) ethoxy) ethyl) methylamino) ethanol. These may be used alone or in combination of two or more. Among these, at least one of tetramethyldiaminohexane, pentamethyldiethylenetriamine, di-tert-butylethylenediamine, triethylenetetramine, and pentaethylenehexamine is particularly high in the effect of suppressing the dissolution of the resin of the photosensitive layer. Is preferred, and at least one of triethylenetetramine and pentaethylenehexamine is particularly preferred.

The content of the nitrogen compound in the developer of the present invention is preferably 0.1 to 50% by mass,
2-5 mass% is more preferable. If the content is less than 0.1% by mass, it may not be possible to effectively suppress the resin in the photosensitive layer from being gradually dissolved, while if it exceeds 50% by mass, the resin in the photosensitive layer may not be dissolved. Oversuppressed,
The photosensitive layer may not be removed efficiently.

-Compound Having Aromatic Ring- The compound having an aromatic ring is not particularly limited, but is preferably, for example, at least one of a naphthalene ring and a benzene ring, which is a compound having a surface active function. Is more preferable. Examples of the compound having an aromatic ring include ammonium dibutylnaphthalenesulfonate and ammonium dipropylnaphthalenesulfonate. These may be used alone or in combination of two or more.

The content of the compound having an aromatic ring in the developer of the present invention is preferably 0.1 to 50% by mass, more preferably 0.1 to 50% by mass. If the content is less than 0.1% by mass, the peeling of the photosensitive layer may not proceed smoothly, while if it exceeds 50% by mass, the peeling of the photosensitive layer may be excessive.

-Carbonate- The carbonate is not particularly limited, but a carbonate containing no metal ion such as sodium is particularly preferable in that it is excellent in residue removability when used for development on a TFT semiconductor substrate. Is preferred. Specific examples thereof include ammonium carbonate and tetramethylammonium carbonate. These may be used alone or in combination of two or more.

The content of the carbonate in the developer of the present invention is preferably 0.1 to 50% by mass, and 0.2
-5 mass% is more preferred. When the content is less than 0.1% by mass, the swelling action of the carbonate may be weak and the effect of peeling the photosensitive layer into minute pieces may be low.
When the content is more than mass%, the carbonate has a strong swelling effect, and the peeling of fine particles of the photosensitive layer may not proceed smoothly. In particular,
As the concentration of the carbonate, the nitrogen compound is triethylenetetramine, pentaethylenehexamine, and
When it is at least one of di-tert-butylethylenediamine, 0.05 to 0.2 mol / L is preferable.

-Other Components- In the developer of the present invention, various other components for developing a photoresist, particularly a developer of a pigment-dispersed photoresist, may be incorporated. Examples of the other components include anionic dispersants such as polycarboxylic acid type polymer surfactants and polysulfonic acid type polymer surfactants, nonionic dispersants such as polyoxyethylene / polyoxypropylene block polymers, and the like. And the like.

The content of the other components in the developer is preferably 0.05 to 20% by mass,
0.2-5 mass% is more preferable.

[Method for forming colored image] In the method for forming a colored image of the present invention, a predetermined photosensitive layer is formed on a substrate, exposed and developed to form a colored image.

-Formation of Photosensitive Layer- The photosensitive layer is alkali-developable and is preferably formed of the following colored image forming material.

<Colored Image Forming Material> The colored image forming material is not particularly limited as long as it can be developed with an alkali and has photosensitivity, but it may be a resin, a coloring agent such as a pigment or a dye, a photopolymerizable unsaturated bond. It is preferable to contain a monomer having one or more of the above in the molecule and a photopolymerization initiator.

--Resin-- The resin used in the colored image forming material does not impair the photosensitivity when the photosensitive layer is formed, and has dispersibility of a colorant such as a pigment, film formability, and alkali developability. There is no particular limitation as long as it is one. Examples of such resins include carboxymethyl hydroxyethyl cellulose, cellulosic resins such as hydroxyethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, and the like.
(Meth) acrylic acid (meaning acrylic acid and methacrylic acid. The same applies hereinafter), itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester and other carboxyl group-containing polymerizable monomers and methyl methacrylate,
(Meth) acrylic acid esters such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, styrene, styrene derivatives, copolymers with other polymerizable monomers, etc. preferable.

The maleic acid monoalkyl ester is preferably one having an alkyl carbon number of 1 to 12,
Monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate,
Mono-n-butyl maleate, Mono-n-hexyl maleate, Mono-n-octyl maleate, Mono 2-maleate
Examples thereof include ethylhexyl, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like. As the styrene derivative, α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-
4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like can be mentioned.

As the resin, a resin having a photopolymerizable unsaturated bond may be used for the purpose of improving photosensitivity. Preferable specific examples of such a resin include oxirane such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and monoalkyl glycidyl ether itaconic acid in a high acid value carboxyl group-containing resin. Compounds each having one ring and one ethylenically unsaturated bond, allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
A resin obtained by reacting a hydroxyl group such as N-methylolacrylamide with a compound having one ethylenically unsaturated bond (unsaturated alcohol), a resin obtained by reacting a carboxyl group-containing resin having a hydroxyl group with a free isocyanate group-containing unsaturated compound , A resin obtained by reacting a polybasic acid anhydride with an addition reaction product of an epoxy resin and an unsaturated carboxylic acid, or a hydroxyl group-containing addition reaction product of a conjugated diene polymer or a conjugated diene copolymer with an unsaturated dicarboxylic acid anhydride Examples thereof include resins obtained by reacting a polymerizable monomer.

The unsaturated equivalent of the resin is 600 to
3000 is preferable and 800-2000 is more preferable. If the unsaturated equivalent is less than 600, it may be partially cured when the photosensitive material is prepared, particularly when the pigment is dispersed in the resin, while if it exceeds 3000, the photosensitivity is improved by the introduction of unsaturated groups. The effect may be reduced. still,
The "unsaturated equivalent weight" refers to the molecular weight of the resin per unsaturated bond.

The above resin has an acid value of 20 to 300 from the viewpoint that the colored image forming material has an alkali developability after exposure.
Is preferable, 40 to 200 is preferable, and 60 to 150 is particularly preferable. If the acid value is less than 20, the alkali developability may decrease, while if it exceeds 300, the shape of the image pattern after alkali development may be unclear.

The weight average molecular weight of the resin is 1,
500 to 200,000 is preferable, 5,000 to 10
50,000 is more preferable, 10,000 to 50,000
0 is more preferable. The weight average molecular weight is 1,500.
If it is less than 200, the dispersion stability of the colorant such as a pigment may be lowered, while if it exceeds 200,000, the viscosity is high when the colored image-forming material is prepared, and the coatability, particularly when spin coating is performed. The coating property of may deteriorate. The "weight average molecular weight" is measured by gel permeation chromatography and converted by using a calibration curve of standard polystyrene.

The resin has an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000.
The resin having a structure represented by at least one of the following general formula (I) and general formula (II) as a repeating unit is preferable.

[0027]

[Chemical 1]

However, in the general formula (I), R ² represents at least one of a hydrogen atom and a methyl group, and R ³ represents at least a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group. Represents either.

[0029]

[Chemical 2]

However, in the general formula (II), R ⁴ represents an alkyl group having 1 to 12 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a photoreactive unsaturated bond. It represents at least one of the groups having.

The molar ratio of the structures represented by the general formulas (I) and (II) in the resin (structure represented by the general formula (I) / structure represented by the general formula (II)). ) Is 1 / in terms of pigment dispersion stability and photosensitivity.
It is preferably 1 to 5/1 (molar ratio).

The resin having the structure represented by the general formula (I) and the structure represented by the general formula (II) as a repeating unit can be produced, for example, by the structure represented by the general formula (I). A resin precursor having as a repeating unit, unsaturated alcohols (allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyacrylate, 2-hydroxymethacrylate, N-methylol Acrylamide) and the like, and a compound having one oxirane ring and one ethylenically unsaturated bond in the precursor of the resin having the structure represented by the general formula (I) as a repeating unit (glycidyl). Methacrylate, glycidyl acrylate, allyl glycidyl ether, α-E Glycidyl acrylate, crotonyl glycidyl ether, and a method of producing by addition reaction of itaconic acid monoalkyl monoglycidyl ester).

The precursor of the resin having the structure represented by the general formula (I) or the general formula (II) as a repeating unit comprises styrene or a derivative thereof and a maleic acid monoalkyl ester (half ester of maleic acid). It can be obtained by a method such as copolymerization. Examples of the styrene derivative include α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene and 2-methoxy-4.
-Hydroxystyrene, 2-hydroxy-4-methylstyrene and the like can be mentioned. Examples of maleic acid monoalkyl esters include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate, mono-n-hexyl maleate, and maleic acid. Mono-
n-octyl, mono-2-ethylhexyl maleate,
Examples include mono-n-nonyl maleate and mono-n-dodecyl maleate.

As the resin, a resin having a structure represented by at least one of the general formula (I) and the general formula (II) as a repeating unit may be used in combination with other resins. The other resin is not particularly limited as long as it is a resin other than the resin having the structure represented by at least one of the general formula (I) and the general formula (II) as a repeating unit, but an acrylic resin, Epoxy resin, urethane resin, melamine resin and the like are preferable. The content of the other resin in 100 parts by mass of the resin is preferably 50 parts by mass or less.

The content of the resin in the colored image-forming material is preferably 10 to 85% by mass, and 20 to 6 is preferable.
0 mass% is more preferable, and 25 to 50 mass% is still more preferable. If the content is less than 10% by mass, the dispersion stability of the pigment may decrease, while if it exceeds 85% by mass, the viscosity when the photosensitive solution is prepared becomes high, and the coating property, particularly spin. The coatability at the time of coating may decrease.

--Coloring Agents such as Pigments and Dyes-- Examples of the coloring agents include pigments such as inorganic pigments and organic pigments and dyes. Among these, pigments are preferable, and black carbon black (inorganic pigment) and organic pigments are particularly preferable in terms of rich color tone. As the organic pigment, for example, azo-based, phthalocyanine-based, indigo-based,
Examples thereof include anthraquinone type, perylene type, quinacridone type, methine / azomethine type, isoindolinone type and the like. When a color filter is manufactured as described below, each pigment system suitable for colored images such as red, green, blue and black is used.

As the red colored image, a single red pigment system may be used, or a yellow pigment system may be mixed with the red pigment system for toning. Examples of the red pigment type include C.I. I. Pigment Red 9,
123, 155, 168, 177, 180, 217, 2
20, 224 and the like. Examples of the yellow pigment type include C.I. I. Pigment Yellow 20, 24, 83, 93, 109, 110, 11
7, 125, 139, 147, 154 and the like.
These red pigment type and yellow pigment type may be used alone or in combination of two or more kinds. When the red pigment system and the yellow pigment system are mixed and used, it is preferable to use the yellow pigment system in 50 parts by mass or less based on 100 parts by mass of the total amount of the red pigment system and the yellow pigment system. .

As the green colored image, a single green pigment system may be used, or the above yellow pigment system may be mixed with the green pigment system for toning. Examples of the green pigment type include C.I. I. Pigment Green 7, 36, 37 and the like. These green pigment type and yellow pigment type may be used alone or in combination of two or more kinds. When the green pigment system and the yellow pigment system are mixed and used, the yellow pigment system is used in an amount of 50 parts by weight based on 100 parts by mass of the total amount of the green pigment system and the yellow pigment system.
It is preferably used in an amount of not more than parts by mass.

As a blue colored image, a single blue pigment system may be used, or a violet pigment system may be mixed with a blue pigment system for toning. Examples of the blue pigment type include C.I. I. Pigment Blue 1
5, 15: 3, 15: 4, 15: 6, 22, 60 and the like. Examples of purple pigments include C.I. I. Pigment Violet 19, 2
3, 29, 37, 50 and the like. These blue pigment systems and purple pigment systems may be used alone or in combination.
You may use together more than one kind. When the blue pigment system and the purple pigment system are mixed and used, the purple pigment system is used in an amount of 5 parts by mass per 100 parts by mass of the total amount of the blue pigment system and the purple pigment system.
It is preferably used in an amount of 0 parts by weight or less.

Examples of black colored images include black pigments such as carbon black, graphite, titanium carbon, black iron, and manganese dioxide.

The content of the pigment in the colored image forming material is preferably 5 to 50% by mass, and 10 to 10% by mass.
40 mass% is more preferable, and 15-30 mass% is still more preferable. If the content of the pigment is less than 5% by mass, the color density of the image may be low, whereas if it exceeds 50% by mass, the photosensitivity may be lowered.

--- Monomer having at least one photopolymerizable unsaturated bond in the molecule-- Among the monomers having at least one photopolymerizable unsaturated bond in the molecule, one photopolymerizable unsaturated bond is present in the molecule. There is no particular limitation on the monomer having each, for example, alkyl methacrylate such as methyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate, alkyl acrylate such as methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and aralkyl methacrylate such as benzyl methacrylate. , Aralkyl acrylates such as benzyl acrylate, alkoxyalkyl methacrylates such as butoxyethyl methacrylate, alkoxyalkyl acrylates such as butoxyethyl acrylate, N, N-dimethylaminoethyl Aminoalkyl methacrylate such as methacrylate, N,
Aminoalkyl acrylates such as N-dimethylaminoethyl acrylate, methacrylic acid esters of (diethylene glycol ethyl ether), methacrylic acid esters of (triethylene glycol butyl ether), and methacrylic acid esters of (dipropylene glycol methyl ether) (polyalkylene glycol Methacrylic acid ester of (alkyl ether), acrylic acid ester of (diethylene glycol ethyl ether), acrylic acid ester of (triethylene glycol butyl ether),
Acrylic ester of (polyalkylene glycol alkyl ether) such as acrylic acid ester of (dipropylene glycol methyl ether), Methacrylic acid ester of (polyalkylene glycol aryl ether) such as methacrylic acid ester of (hexaethylene glycol phenyl ether), Acrylic ester of (polyalkylene glycol aryl ether) such as acrylic ester of (hexaethylene glycol phenyl ether), dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate, methoxylated cyclodecatriene methacrylate, iso Bornyl acrylate, methoxylated cyclodecatriene acrylate, glycerol methacrylate, glycerol acrylate, hep Fluorinated alkyl methacrylates such as decafluoro decyl methacrylate, fluorinated alkyl acrylates such as hept decafluoro decyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and the like.

Of the monomers having at least one photopolymerizable unsaturated bond in the molecule, the monomer having at least two photopolymerizable unsaturated bonds in the molecule is not particularly limited, and examples thereof include bisphenol A. Dimethacrylate, 1,
4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane tri Methacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate,
1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate,
Examples include trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule further include a diacrylate of an alkylene oxide adduct of bisphenol A represented by the following general formula (A) and a general formula (B). Bisphenol A epichlorohydrin modified product and acrylic acid addition esterified product, bisphenol A dimethacrylate,
1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, alkylene oxide adduct of phosphoric acid represented by the general formula (C) Diacrylate, an epichlorin modified product of phthalic acid represented by the general formula (D) and an addition ester of acrylic acid, a diacrylate of polyethylene glycol, a dimethacrylate of polypropylene glycol, a tetraethylene glycol diacrylate, a general formula (E) Indicated by 1,6
-Epichlorin modified product of hexanediol and addition esterified product of acrylic acid (having two akyryl groups in one molecule), trimethylolpropane triacrylate, pentaerythritol triacrylate, and phosphoric acid of the general formula (f) Triacrylate of alkyne oxide adduct, triacrylate of alkylene oxide adduct of trimethylolpropane represented by general formula (g), tris (tacryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipenta Examples thereof include erythritol hexaacrylate and dipentaerythritol pentaacrylate. These monomers can be used alone or in combination of two or more kinds. General formula (A)

[0045]

[Chemical 3]

However, in the general formula (A), R represents an ethylene group or a propylene group, m and n are each independently,
It represents an integer of 1 to 20. General formula (B)

[0047]

[Chemical 4]

However, in the general formula (B), m and n each independently represent an integer of 1 to 10. General formula (C)

[0049]

[Chemical 5]

However, in the general formula (C), R represents an ethylene group or a propylene group, and m and n each independently represent an integer of 1 to 20. General formula (D)

[0051]

[Chemical 6]

However, in the general formula (D), m and n each independently represent an integer of 1 to 10. General formula (E)

[0053]

[Chemical 7]

However, in the general formula (E), m and n each independently represent an integer of 1 to 20. General formula (F)

[0055]

[Chemical 8] However, in the general formula (F), R represents an ethylene group or a propylene group, and three m are each independently 1 to 20.
Represents the integer. General formula (G)

[0056]

[Chemical 9]

However, in the general formula (G), R represents an ethylene group or a propylene group, and m, m ′ and m ″ each independently represent an integer of 1 to 20.

The content of the monomer having two or more photopolymerizable unsaturated bonds in the molecule in the colored image-forming material is preferably 2 to 50% by mass, more preferably 5 to 40% by mass. -30 mass% is more preferred. If the content is less than 2% by mass, the photosensitivity may decrease, while if it exceeds 50% by mass, the dispersion stability of the pigment may decrease.

--Photopolymerization Initiator-- Examples of the photopolymerization initiator used in the colored image forming material include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-.
4'-dimethylaminobenzophenone, benzyl, 2,
2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone,
1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, t-butylanthraquinone, 1
-Chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10
-Phenanthraquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, and 2- (o-chlorophenyl)-
Examples include 4,5-diphenylimidazole dimer. These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator in the colored image forming material is preferably 0.01 to 20% by mass, more preferably 2 to 15% by mass, and further preferably 5 to 10% by mass. The content of the photopolymerization initiator is 0.
If it is less than 01% by mass, the photosensitivity may decrease, while if it exceeds 20% by mass, the adhesiveness may decrease.

—Other Components—— The colored image-forming material contains a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing dark reaction, and adhesion to the substrate. Titanate coupling agent for improving the (vinyl group, epoxy group, amino group, silane coupling agent having a mercapto group or isopropyl trimethacryloyl titanate, diisopropyl isostearoyl-4-aminobenzoyl titanate, etc.),
Surfactants for improving the smoothness of the film (fluorine-based,
If necessary, various additives such as ultraviolet absorbers and antioxidants can be appropriately used.

<Method for Forming Photosensitive Layer> The method for forming the photosensitive layer on the substrate is not particularly limited.
A method for preparing a photosensitive layer coating solution by mixing the components of a colored image forming material and an appropriate organic solvent, and directly coating the photosensitive layer coating solution on the substrate, and separately coating the photosensitive layer coating solution on a temporary support. A method of forming a photosensitive layer by laminating it on a substrate after forming the film is preferable.

<< Preparation Method of Coating Liquid for Photosensitive Layer >> An example of the method for preparing the coating liquid for the photosensitive layer will be described below. For example,
A colored image forming material such as a pigment or a resin is mixed with an organic solvent and, if necessary, a dispersant or the like and dispersed. At this time, the mixing is preferably carried out by a dispersion treatment by kneading using a dispersing / kneading device such as an ultrasonic disperser, a triple roll, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader. Further, with respect to 100 parts by mass of the pigment,
It is preferable to mix at least 20 parts by mass of the resin. If the amount of resin is too small, the dispersion stability of the pigment tends to decrease. Similarly, the total amount of the organic solvent may be used when the pigment is dispersed, or a part of the organic solvent may be added after the dispersion. However, the organic solvent is 1% of the total amount of pigment and resin when dispersed.
It is preferable to use at least 100 parts by mass at the time of dispersion with respect to 00 parts by mass. If the amount is less than 100 parts by mass, the viscosity at the time of dispersion is too high, and the dispersion may be difficult especially when the dispersion is performed by a ball mill, a sand mill, a peas mill or the like.

To prepare the photosensitive solution for the photosensitive layer, a monomer having two or more photopolymerizable unsaturated bonds in the molecule and a photopolymerization initiator are further mixed, which are added before the dispersion treatment. Or may be mixed after the dispersion treatment. The resin and the organic solvent may not be entirely used at the time of the dispersion, and the rest may be mixed later, and it is particularly preferable to mix them at the time of producing the photosensitive liquid for the photosensitive layer.

Examples of the organic solvent include ketone compounds, alkylene glycol ether compounds, alcohol compounds and aromatic compounds. Specific examples of the ketone compound include acetone, methyl ethyl ketone, cyclohexanone, dioxane, and the like, and as the alkylene glycol ether compound, methyl cellosolve, ethyl cellosolve, butyzocellosolve, methyl cellosolve acetate, ethyl cellosolve acetate,
Butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Propylene glycol monomethyl ether acetate D and the like, polyethylene glycol alkyl ether acetate compound, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate,
Diethylene glycol propyl ether acetate, diethylene glycol iso-propyl ether acetate, diethylene glycol butyl ether acetate,
Diethylene glycol tert-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol iso-propyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol tert-butyl ether acetate, etc. Examples of alcohol compounds include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, and 3-methyl-3.
Examples of the aromatic compound include benzene, toluene, xylene, N-methyl-2-pyrrolidone, and N-hydroxymethyl-2-pyrrolidone. Other, 3
Examples include organic solvents such as -methyl-3-methoxybutyl acetate and ethyl acetate. These may be used alone or in combination of two or more.

The organic solvent has a total solid content of 5 to 4 including the resin, the pigment, the monomer containing at least one photopolymerizable unsaturated bond in the molecule and the photopolymerization initiator in the photosensitive layer coating solution.
It is preferably used so as to be in the range of 0% by mass.
When the total solid content exceeds 40% by mass, the viscosity becomes high,
Applicability may deteriorate, while total solid content is 5% by mass
If it is less than the above range, the viscosity may be low and the coatability may be poor.

Examples of the dispersant include anionic dispersants such as polycarboxylic acid type polymer surfactants and polysulfonic acid type polymer surfactants, and nonionic dispersions such as polyoxyethylene / polyoxypropylene block polymers. Agents, anthraquinone-based, perylene-based, phthalocyanine-based, quinacdrine-based organic dyes, and the like, derivatives of organic dyes in which a carboxyl group, a sulfonate group, a carboxylic acid amide group, a substituent such as a hydroxyl group is introduced, and the like, and the dispersant Is preferable because the dispersibility and dispersion stability of the pigment are improved. These pigment dispersants and organic dye derivatives are preferably used in an amount of 50 parts by mass or less relative to 100 parts by mass of the pigment. If it exceeds 50 parts by mass, the chromaticity may shift.

The method of applying the photosensitive layer coating solution is not particularly limited, but for example, roll coater coating,
Examples thereof include spin coater coating, spray coating, whaler coating, dip coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, and air knife coater coating. After application
It is preferable to dry at a temperature of 50 to 130 ° C. for 1 to 30 minutes.

The thickness of the photosensitive layer varies depending on the application and cannot be generally stated, but is preferably 0.1 to 300 μm. For color filter applications,
0.2-5 micrometers is preferable.

The material of the substrate is selected depending on the application, but for example, transparent glass plate such as white plate glass, blue plate glass, silica-coated blue plate glass, polyester resin,
Sheets made of synthetic resin such as polycarbonate resin, acrylic resin, vinyl chloride resin, films or plates, aluminum plates, copper plates, nickel plates, metal plates such as stainless plates, other ceramic plates, and semiconductor substrates having photoelectric conversion elements Can be mentioned. A black matrix may be previously formed on these substrates by vapor deposition of chromium or the like.

When the photosensitive layer is formed on a temporary support by laminating it on a substrate after forming the film on the temporary support, the temporary support is superposed on the substrate and pressure-bonded through a roller to expose the photosensitive layer on the substrate. It is preferred to stack the layers. At this time, it is preferable to heat the roller to some extent. Moreover, it is preferable to perform the pressure bonding under reduced pressure. The temporary support is preferably peeled off after the photosensitive layer is laminated on the substrate. Examples of the material of the temporary support include polyethylene film, acrylic resin film, polyester film and the like.

-Formation of Other Layers- In the present invention, in addition to the above-mentioned photosensitive layer, a thermoplastic resin layer, an oxygen blocking layer and the like can be formed as required.

--Thermoplastic Resin Layer-- The thermoplastic resin layer is provided as the first layer on the temporary support, contains the thermoplastic resin, and optionally other components. The thermoplastic resin is preferably an alkali-soluble resin having a substantial softening point of 80 ° C. or lower. Examples of the thermoplastic resin having a softening point of 80 ° C. or lower include saponified products of ethylene and an acrylic acid ester copolymer, saponified products of styrene and a (meth) acrylic acid ester copolymer, and vinyltoluene (meth). ) Saponified products of acrylic acid ester copolymers, poly (meth) acrylic acid esters, and saponified products of (meth) acrylic acid ester copolymers of butyl (meth) acrylate and vinyl acetate and the like. These may be used alone or in combination of two or more. Furthermore, "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Federation, published by Industrial Research Board, 1968)
Among the organic polymers having a softening point of about 80 ° C. or less, which are described in October 25, 2004, resins soluble in an alkaline aqueous solution are also preferable.

Further, even if an organic polymer substance having a softening point of 80 ° C. or higher is added to the organic polymer substance, various plasticizers compatible with the organic polymer substance are added to substantially soften it. The point can be lowered to 80 ° C. or lower for use. Examples of the plasticizer include the same plasticizers as those usable in the photocurable composition described above.

When the organic polymer material is used, various polymers, supercooling substances, and adhesion improving agents are used in order to adjust the adhesive force with a temporary support described later, within the range where the substantial softening point does not exceed 80 ° C. Agents, surfactants, release agents and the like can also be added. The thermoplastic resin layer is prepared by dissolving the thermoplastic resin and optionally other components in an organic solvent to prepare a coating liquid (thermoplastic resin layer coating liquid). It can be formed by coating on a temporary support by a coating method.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether. Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; Glycol methyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol ethyl ether acetate: toluene, xylene and the like aromatic hydrocarbons; methyl ethyl ketone, cyclohexanone, 4-hydroxy -
Ketones such as 4-methyl-2-pentanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-2-methylbutanoate,
Methyl 3-methoxypropionate, ethyl 3-methoquinopropionate, methyl 3-ethoxypropionate, 3-
Esters such as ethyl ethoxypropionate, ethyl acetate and butyl acetate; and the like. These organic solvents may be used alone or in combination of two or more.

Among these, in view of solubility of each component and film forming property, glycol esters such as ethylene glycol dimethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, ethyl 2-hydroxypropionate, and 3 Particularly preferred are esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate, and diethylene glycols such as diethylene glycol dimethyl ether.

Furthermore, N-methylformamide, N, N-
Dimethylformamide, N-methylformanilide, N
-Methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
It is also possible to add a high boiling point solvent such as -octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate.

The thickness of the thermoplastic resin layer is 6 to
100 μm is preferable, and 6 to 50 μm is more preferable.

--Oxygen Barrier Layer-- The oxygen barrier layer contains a resin component that can be dispersed and dissolved in water or an aqueous alkali solution, and may further contain other components such as a surfactant, if necessary. . Examples of the resin component contained in the oxygen barrier layer include known resins, for example, JP-A-46-2121 and JP-B-56-40.
No. 824, polyvinyl ether / maleic anhydride polymer, water-soluble salt of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salt of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamides, water-soluble polyamide ,
Examples thereof include water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, water-soluble salts of the group consisting of various starches and the like, styrene / maleic acid copolymers, maleate resins, and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a hydrophilic polymer, and it is preferable to use at least polyvinyl alcohol among the hydrophilic polymers, and it is particularly preferable to use polyvinyl alcohol and polyvinylpyrrolidone in combination.

The polyvinyl alcohol is appropriately selected depending on the intended purpose without any limitation, but the saponification rate is preferably 80% or more. When the polyvinylpyrrolidone is used, its content is preferably 1 to 75% by volume, more preferably 1 to 60% by volume, and 10 to 50% based on the solid content of the oxygen barrier layer.
Volume% is more preferred. If the content is less than 1% by volume, sufficient adhesiveness to the photosensitive resin layer may not be obtained, while if it exceeds 75% by volume, the oxygen barrier ability may decrease.

The oxygen barrier layer is prepared by dissolving and dispersing the resin components and the like in an aqueous solvent to prepare a coating liquid (oxygen barrier layer coating liquid), and applying the above-mentioned heat treatment by a known coating method such as spin coating. It is preferably formed by coating on the plastic resin layer. Examples of the water-based solvent include a solvent containing water such as distilled water as a main component, and if desired, a solvent having a compatibility with water such as alcohol or a salt added thereto within a range not impairing the effects of the present invention.

The thickness of the oxygen barrier layer is 0.1 to 0.1
5 μm is preferable, and 0.5 to 2 μm is more preferable. If the layer thickness is less than 0.1 μm, the oxygen permeability is too high, and the polymerization sensitivity of the photosensitive resin layer may decrease, while if it exceeds 5 μm, it takes a long time during development and removal of the oxygen barrier layer. It may cost.

-Exposure-The exposure of the photosensitive layer formed on the substrate can be suitably carried out by a method of irradiating the photosensitive layer with an actinic ray in an image form, whereby the film in the exposed portion is cured. Can be made. During exposure, an oxygen barrier film such as polyvinyl alcohol is formed on the surface of the film to a thickness of 0.5 to 30 μm,
You may expose from it. As the light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a Langsten lamp, a visible light laser and the like are preferable. Actinic rays are radiated imagewise by pattern exposure through a photomask using these light sources or direct drawing by scanning.

-Development-Development is performed following the exposure. In the present invention, the development is carried out using the developing solution of the present invention. Therefore, the nitrogen compound contained in the developing solution has a role of effectively blocking the acidic group (carboxyl group or the like) in the resin forming the photosensitive layer from being gradually dissolved by the base. Further, the carbonate contained in the developer has a role of entering the photosensitive layer and effectively swelling the photosensitive layer. Further, the compound having an aromatic ring contained in the developer has a role of peeling the swollen photosensitive layer. Therefore, in the portion where the photosensitive layer is desired to be removed, the photosensitive layer can be rapidly peeled by the swelling action of the carbonate while suppressing the gradual dissolution of the photosensitive layer. As a result, it is possible to efficiently form an image with excellent residue removability and good contact resistance.

In the development, the unexposed portion can be removed by a method of spraying a developing solution or immersing in a developing solution to obtain a colored image pattern of a cured film corresponding to an image. After development, post-baking is preferably performed in order to more firmly cure the colored image pattern.
The post-baking temperature is preferably 60 to 280 ° C., and the heating time is more preferably 1 to 60 minutes.

[Method for producing color filter] In the method for producing a color filter of the present invention, a predetermined photosensitive layer is formed on a substrate, exposed and developed to form a plurality of colored images on the same substrate. The formation, exposure, and development of the photosensitive layer are
This is the same as the method for forming the colored image of the present invention. In the method for producing a color filter of the present invention, it is particularly preferable that the formation of the colored image is repeated for colored images of different 3 to 4 colors.

For example, a method of forming red, green, and blue colored images on the black matrix formed by chromium vapor deposition or the like in the same manner as the above-described colored image forming method of the present invention, and a black colored image forming material. After forming a black matrix using the method, a red, green and blue colored image is formed in the same manner as in the colored image forming method of the present invention, and a red color is formed in the same manner as in the colored image forming method of the present invention. After forming colored images of green, blue, and the like, a method of forming a black matrix by using a black image forming material in a gap between these colored images, and the like. The order of forming the red, green and blue colored images is not particularly limited and is arbitrary.

[Manufacturing Method of Array Substrate with Color Filter] In the manufacturing method of the array substrate with a color filter of the present invention, a predetermined photosensitive layer is provided as a TFT (thin film transistor) active matrix substrate (TFT array substrate).
A plurality of colored images are formed on the same TFT array substrate by forming the above, exposing and developing. Formation of the photosensitive layer, exposure,
The development is the same as the method for forming the colored image of the present invention. The TFT active matrix substrate is not particularly limited, and a commonly used one can be used without limitation. For example, a gate signal line and an additional capacitance electrode are formed on an active matrix substrate (array substrate), a gate insulating film is formed on the gate signal line, and a semiconductor layer and a channel protective layer are formed on the active matrix substrate (array substrate). Then, a metal layer and an ITO film are formed by a sputtering method, and these are patterned to form a drain signal line and a source signal line. The method for producing an array substrate with a color filter of the present invention can be suitably carried out, for example, according to the description in JP-A-10-206,888.

In the method of manufacturing the array substrate with a color filter of the present invention, it is preferable that the TFT active matrix substrate is formed of amorphous silicon, a low temperature polysilicon base material, or a continuous grain silicon base material.

According to the method for producing an array substrate with a color filter of the present invention, the development is carried out using the above-mentioned developing solution of the present invention containing a carbonate which does not particularly need to contain metal ions. Even with the above development, the residue removal property of the formed image is excellent, and the contact resistance is good.

[0092]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

-Production of integrated film- Polyethylene terephthalate film (thickness = 75 μm
m) A coating liquid for a thermoplastic resin layer having the following composition on a temporary support,
A coating solution for oxygen barrier layer having the following composition, and a coating solution for photosensitive layer (one type selected from coating solutions K to S for photosensitive layer (shown in Table 1)) are applied and each layer is laminated to form a thermoplastic resin. A layer, an oxygen barrier layer, and a photosensitive layer are sequentially provided and further covered with a protective film to provide a temporary support, a thermoplastic resin layer (dry thickness: 14.6 μm), an oxygen barrier layer (dry thickness: 1.
6 μm) and a film (films K to S) in which the photosensitive layer was integrated. Table 1 below shows the obtained integral film, the coating solution for the photosensitive layer used, and the thickness of the formed photosensitive layer.

[0094]

[Table 1]

[0095] <Composition of coating liquid for thermoplastic resin layer> ・ Vinyl chloride / vinyl acetate copolymer ・ ・ ・ ・ ・ ・ ・ 300 parts by mass -Vinyl chloride-vinyl acetate-maleic acid copolymer ... 80 parts by mass ・ Dibutyl phthalate: 80 parts by mass (Methyl ethyl ketone is added appropriately)

[0096] <Composition of coating liquid for oxygen barrier layer> ・ Polyvinyl alcohol ・ ・ ・ ・ ・ ・ 200 parts by mass (Add water appropriately)

[0097] <Composition of coating liquid K for photosensitive layer> -Benzyl methacrylate / methacrylic acid copolymer--60 parts by mass ・ Pentaerythritol tetraacrylate ・ ・ 40 parts by mass ・ Michler's ketone ・ ・ 3 parts by mass -2- (o-chlorophenyl) -4,5-diphenylamidazyl dimer                                       ..... 3 parts by mass ・ Carbon black ・ ・ ・ ・ 6 parts by mass   (Methyl ethyl ketone is added appropriately)

[0098] <Composition of coating liquid R for photosensitive layer> ・ Benzyl methacrylate / methacrylic acid copolymer: 32 parts by mass ・ Pentaerythritol hexaacrylate ・ ・ ・ ・ 31 parts by mass ・ Photopolymerization initiator ・ ・ ・ ・ ・ ・ 2.5 parts by mass (2-trichloromethyl-5- (p-styrylstyryl) 1,3,4-oxadi Azole) ・ UV absorber ・ ・ ・ ・ ・ ・ ・ ・ ・ 12 parts by mass   (7- (2- (4- (3-hydroxymethylpiperidino) -6-diethylamido No) Triazinylamino) -3-phenylcoumarin ・ Phenothiazine ・ ・ ・ ・ ・ ・ ・ ・ 0.1 parts by mass ・ PR254 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 9.6 parts by mass   (Methyl ethyl ketone is added appropriately)

[0099] <Composition of coating liquid G for photosensitive layer> ・ Benzyl methacrylate / methacrylic acid copolymer ... 30 parts by mass ・ Pentaerythritol hexaacrylate ・ ・ ・ ・ 29 parts by mass ・ Photopolymerization initiator ・ ・ ・ 1.5 parts by mass (2-trichloromethyl-5- (p-styrylstyryl) 1,3,4-oxadi Azole) ・ UV absorber ・ ・ ・ ・ ・ ・ 9.8 parts by mass (7- (2- (4- (3-hydroxymethylpiperidino) -6-diethylamino ) Triazinylamino) -3-phenylcoumarin) ・ PY138 ・ ・ ・ ・ ・ ・ 10.1 parts by mass PG36 ... 20 parts by mass     (Add methyl ethyl ketone as appropriate)

[0100] <Composition of coating liquid B for photosensitive layer> ・ Benzyl methacrylate / methacrylic acid copolymer: 42 parts by mass ・ Pentaerythritol hexaacrylate ・ ・ ・ ・ 32 parts by mass ・ Photopolymerization initiator ・ ・ ・ ・ ・ ・ 1.6 parts by mass (2-trichloromethyl-5- (p-styrylstyryl) 1,3,4-oxadi Azole) ・ Phenothiazine ・ ・ ・ ・ 0.2 parts by mass ・ PB15: 6 ・ ・ ・ ・ ・ ・ 24 parts by mass (Add methyl methyl ketone as appropriate)

[0101] <Composition of coating liquid S for photosensitive layer> Polymer: 24 parts by mass Styrene / maleic acid copolymer benzylamine modified product (copolymerization ratio 68/32) ・ Dipentaerythritol hexaacrylate ・ ・ ・ ・ 20 parts by mass ・ Photopolymerization initiator ・ ・ ・ ・ ・ ・ 1 part by mass (IRG184 (CAS947-19-3) ・ UV absorber ・ ・ ・ ・ 12 parts by mass (7- (2- (4- (3-hydroxymethylpiperidino) -6-diethylamino ) Triazinylamino) -3-phenylcoumarin (Methyl ethyl ketone is added appropriately)

The active matrix substrates of Examples 1 to 10 and Comparative Example 1 were manufactured in accordance with the description of JP-A-10-206,888.

(Example 1) -Washing of TFT array substrate-A TFT array substrate having a length of 320 mm and a width of 400 mm was ultrasonically cleaned for 1 minute in ultrapure at room temperature, then drained by air blow and dried for cleaning.

-Formation of Resin Layer- The protective film on the film R (OD of the photosensitive resin layer at a wavelength of 365 nm of 1.5) was peeled off, and the temperature was set to 130.
It was laminated on the TFT array substrate at a temperature of 100 ° C., a linear pressure of 100 N / cm and a conveying speed of 1.0 m / min. After that, the distance between the lower surface of the exposure mask and the film R is measured with a proximity type exposure machine having an ultra-high pressure mercury lamp (this distance may be referred to as a “proxy amount” in this embodiment).
Was set to 60 μm, and after pattern exposure with an exposure dose of 30 mJ / cm ² , the solution was exposed to 35 ° C. at 38 ° C. with a developer P1 having the following composition.
After shower development for 2 seconds, the thermoplastic resin layer and the oxygen barrier layer were removed.

<Composition of developer P1> ・ Ultrapure water: 97 parts by mass ・ Triethanolamine: 3 parts by mass (Na concentration: 12 ppb)

Subsequently, with a developer C1 having the following composition,
The photosensitive layer was developed by shower development at 33 ° C. for 40 seconds to obtain a pattern image.

[0107] <Composition of developer C1> ・ Polyoxyethylene (N = 13) naphthyl ether: 5 g / L ・ Ammonium carbonate ・ ・ ・ ・ 6.5g / L ・ Ammonium dibutylnaphthalene sulfonate ・ ・ ・ ・ ・ ・ 9.2g / L ・ Tetramethyldiaminohexane ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.4g / L The rest (water)

Subsequently, a treatment liquid C2 having the following composition was added.
Shower treatment and brush treatment were performed at 33 ° C. for 20 seconds.

[0109] <Composition of treatment liquid C2> ・ Triethanolamine: 8 g / L Polyoxyethylene (N = 15) cetyl ether ... 6g / L The rest: water

Further, subsequently, from the resin layer side to the TFT substrate, after post-exposure with light of 500 mJ / cm ² with an ultra-high pressure mercury lamp, a warm air circulation type clean open was performed.
A heat treatment was performed at 220 ° C. for 130 minutes to produce a colored image.
The residue in the contact hole portion of the obtained colored image was observed with a scanning electron microscope and evaluated according to the following evaluation criteria. Moreover, the contact resistance was measured. The results are shown in Table 2.

-Evaluation criteria- ・ No development residue was found in the unexposed area ... ・ Slight development residue was observed in the unexposed area .... ○ ・ Some development residue was found in the unexposed area ・ ・ ・ △ ・ A large amount of development residue was observed in the unexposed area.

(Example 2) <Formation of resin layer> of Example 1
In the same manner as in Example 1, except that the tetramethyldiaminohexane in the “Developer C1 composition” used for development was replaced with di-tert-butylethylenediamine, a colored image was produced in the same manner as in Example 1. And observe
The measurement was performed. The results are shown in Table 2.

(Example 3) <Formation of resin layer> of Example 1
A colored image was produced in the same manner as in Example 1 except that tetrabutyldiethylenetriamine was used in place of tetramethyldiaminohexane in the “composition of developer C1” used for development, and observation was performed in the same manner as in Example 1.・ Measured. The results are shown in Table 2.

(Example 4) <Formation of resin layer> of Example 1
In the above, a colored image was produced in the same manner as in Example 1 except that tetramethyldiaminohexane in "Composition of developer C1" used for development was replaced with triethylenetetramine, and observed in the same manner as in Example 1.・ Measured.
The results are shown in Table 2.

(Example 5) <Formation of resin layer> of Example 1
A colored image was produced in the same manner as in Example 1 except that pentaethylenehexamine was used in place of tetramethyldiaminohexane in "Composition of developer C1" used for development, and observation was performed in the same manner as in Example 1.・ Evaluated. The results are shown in Table 2.

(Example 6) <Formation of resin layer> of Example 1
In the above, tetramethyldiaminohexane in the "composition of developer C1" used for the development was replaced with pentakis (2-
A colored image was produced in the same manner as in Example 1 except that hydroxypropyl) diethylenetriamine was used, and observation and evaluation were performed in the same manner as in Example 1. The results are shown in Table 2.

Example 7 <Formation of Resin Layer> of Example 1
In the above, a colored image was produced in the same manner as in Example 1 except that tetramethyldiaminohexane in "composition of developer C1" used for development was replaced with pentamethyldiethylenetriamine, and observed in the same manner as in Example 1.・ Evaluated. The results are shown in Table 2.

Example 8 <Formation of Resin Layer> of Example 1
In, in the "composition of the developer C1" used for the development, tetramethyldiaminohexane was added to 2- (2- (2-
A colored image was produced in the same manner as in Example 1 except that dimethylamino) ethoxy) ethyl) methylamino) ethanol was used, and observation and evaluation were performed in the same manner as in Example 1. The results are shown in Table 2.

Example 9 <Formation of Resin Layer> of Example 1
A colored image was produced in the same manner as in Example 1 except that the tetramethyldiaminohexane in the "composition of the developing solution C1" used for development was replaced with hexamethylenetetramine, and the observation was performed in the same manner as in Example 1.・ Evaluated. The results are shown in Table 2.

(Example 10) In the same manner as in Example 1 except that the ammonium carbonate in the "composition of the developing solution C1" used for the development in "Formation of the resin layer" in Example 1 was changed to sodium carbonate. Example 1 to produce a colored image by
Observation and evaluation were performed in the same manner as in. The results are shown in Table 2.

(Example 11) In Example 1, the film R was replaced with the film K, and "Developer C1" was used for development.
Except that the tetramethyldiaminohexane in "composition of" was replaced with di-tert-butylethylenediamine,
A colored image was produced in the same manner as in Example 1, and observed and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 12) In Example 1, the film R was replaced with the film G, and "Developer C1" was used for development.
Except that the tetramethyldiaminohexane in "composition of" was replaced with di-tert-butylethylenediamine,
A colored image was produced in the same manner as in Example 1, and observed and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 13) In Example 1, the film R was replaced with the film B, and the "Developer C1" used in the development was used.
Except that the tetramethyldiaminohexane in "composition of" was replaced with di-tert-butylethylenediamine,
A colored image was produced in the same manner as in Example 1, and observed and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 14) In Example 1, the film R was replaced with the film S, and the "developing solution C1" used in the development was used.
Except that the tetramethyldiaminohexane in "composition of" was replaced with di-tert-butylethylenediamine,
A colored image was produced in the same manner as in Example 1, and observed and evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1 <Formation of Resin Layer> of Example 1
In the above, a colored image was produced in the same manner as in Example 1 except that tetramethyldiaminohexane in the “composition of the developing solution C1” used for development was replaced with diethanolamine, and observation and evaluation were performed in the same manner as in Example 1. I went. The results are shown in Table 2.

[0126]

[Table 2]

[0127]

According to the present invention, a developer capable of forming a colored image having excellent residue removability and good contact resistance even when it does not contain a metal ion, and a colored image using the developer. Forming method, color filter manufacturing method,
And the manufacturing method of the array substrate with the color filter can be provided.

Continued front page    (72) Inventor Mitsutoshi Tanaka             200, Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo             Within Film Co., Ltd. F term (reference) 2H048 BA02 BA45 BA47 BA48 BB02                       BB42                 2H096 AA28 AA30 BA05 GA08 GA17                       HA30

Claims (11)

[Claims] 1. A developing solution containing a nitrogen compound having two or more nitrogen atoms in the molecule, a compound having an aromatic ring, and a carbonate. 2. The developer according to claim 1, wherein the nitrogen compound containing two or more nitrogen atoms in the molecule is at least one of triethylenetetramine, pentaethylenehexamine, and di-tert-butylethylenediamine. . 3. The developer according to claim 1, wherein the aromatic ring is at least one of a naphthalene ring and a benzene ring. 4. The developer according to claim 1, wherein the carbonate does not contain a metal ion. 5. The developing solution according to claim 1, wherein the content of the compound having an aromatic ring in the developing solution is 0.1 to 50 mass%. 6. The developing solution according to claim 1, wherein the content of the nitrogen compound containing two or more nitrogen atoms in the molecule in the developing solution is 0.1 to 50 mass%. 7. The content of carbonate in the developing solution is 0.
The developing solution according to claim 1, which is 1 to 50% by mass. 8. A method for forming a colored image, wherein at least a photosensitive resin layer capable of alkali development is formed on a substrate, exposed and developed to form a colored image.
7. A method for forming a colored image, which is performed using the developer according to any one of 1 to 7. 9. A colored image formation in which the photosensitive resin layer contains a resin having an acid value of 20 to 300, a pigment, a monomer containing at least one photopolymerizable unsaturated bond in the molecule, and a photopolymerization initiator. The method for forming a colored image according to claim 8, which is formed of a material. 10. A method for producing a color filter, wherein at least a photosensitive resin layer capable of alkali development is formed on a substrate, exposed and developed to form a plurality of colored images on the same substrate. A method for producing a color filter, which is performed using the developer according to any one of claims 1 to 7. 11. A method of manufacturing an array substrate with a color filter, wherein at least a photosensitive resin layer capable of alkali development is formed on a TFT array substrate, exposed and developed to form a plurality of colored images on the same TFT array substrate. Method,
Development is performed using the developing solution in any one of Claim 1 to 7, The manufacturing method of the array substrate with a color filter characterized by the above-mentioned.