JP2000075501A - Developer, production of color image using the same and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer for color image forming material improved in all points of developing time, resolution and development residue, which are problems of a developer for a photosensitive material having dispersed pigment, a producing method of a color image using the developer and a producing method of a color filter using the developer. SOLUTION: The developer is prepared by containing a compound exhibiting basicity, an alkyl phenol based surfactant and an alkyl ether based surfactant. The producing method of the color image contains a color image forming process for laminating a layer composed of an alkali developable photosensitive color image forming material on a substrate and exposing and developing and as a developer used at the time of developing, the said developer is used. The producing method of a color filter is to form plural color images on the same substrate by the producing method of the color image.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a developer, a method for producing a colored image using the same, and a method for producing a color filter.

[0002]

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

[0003] Recently, attention has been paid to a method of using a photosensitive material in which a pigment is dispersed for the purpose of improving heat resistance and light resistance, and much research has been conducted. According to this method, the manufacturing method is also simplified. It is known that the obtained color filter is also stable and has a long life. The production of a colored image using a photoresist in which such a pigment is dispersed has been exalted in terms of the stability of the obtained image and the long life.

However, conventionally, the technique of developing a photoresist in which a pigment is dispersed is difficult, and particularly, the development time, resolution,
It was difficult to satisfy all the problems of the development residue.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a developing solution for a photosensitive material in which a pigment is dispersed.
It is an object of the present invention to provide a developer for a colored image forming material which improves both resolution and development residue and solves the problems of the prior art.

Another object of the present invention is to provide a method for producing a colored image using the developer.

Another object of the present invention is to provide a method for producing a color filter using the developer.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a developer comprising a compound exhibiting basicity, an alkylphenol-based surfactant and an alkylether-based surfactant.

[0009] The present invention also relates to a compound having at least one inorganic alkali compound selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate and potassium metasilicate. It relates to a certain developer.

According to the present invention, an alkylphenol-based surfactant is represented by the following general formula (1):

[0011]

Embedded image (Wherein, R ¹ represents an aliphatic hydrocarbon group having 1 to 19 carbon atoms, t is 0 or 1, and n is an integer of 1 to 50). .

According to the present invention, an alkyl ether surfactant is represented by the following general formula (2):

[0013]

Embedded image (Wherein, R ² represents an alkyl group having 1 to 100 carbon atoms;
m is an integer of 1 to 50. ) Is a compound represented by formula (1).

According to the present invention, there is provided a method for producing a colored image, which comprises laminating a layer composed of a photosensitive colored image-forming material capable of developing with an alkali on a substrate and exposing and developing the colored image-forming material. The present invention relates to a method for producing a colored image, wherein any one of the above-mentioned developing solutions is used as a developing solution.

The present invention also relates to a photosensitive colored image-forming material which is alkali-developable and has a resin having an acid value of 20 to 300, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator. The present invention relates to a method for producing a colored image containing an agent.

The present invention also relates to a method for producing a color filter, wherein a plurality of colored images are produced on the same substrate by any one of the above-mentioned methods for producing a colored image.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The developing solution of the present invention is preferably used for developing a photoresist and for developing a pigment-dispersed photoresist.

In the present invention, the basic compound is dissolved or dispersed in water. As the compound showing basicity, an inorganic alkali compound or an organic alkali compound is used, and an inorganic alkali compound is preferable in terms of handling. Examples of the inorganic alkali compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate and potassium metasilicate, and potassium hydroxide and potassium carbonate are most preferred. Two or more inorganic alkali compounds can be used in combination.

The organic alkali compounds include triethanolamine, diethanolamine, butylamine, phenylhydrazine, tetramethylammonium hydroxide and the like.

The content of the compound showing basicity is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the total amount of the developing solution. It is particularly preferred that the amount be 0.1 to 10 parts by weight. If the content of the inorganic alkali compound is too small, the resolution tends to be insufficient. If the content is too large, the entire photoresist tends to peel off from the substrate and cannot be selectively removed.

The developer of the present invention further contains, as essential components, an alkylphenol-based surfactant and an alkylether-based surfactant, preferably in a dissolved state.

The content of the alkylphenol surfactant is preferably 0.005 to 20% by weight, more preferably 0.01 to 20% by weight, and more preferably 0.05 to 20% by weight, based on the total amount of the developer. The content is more preferably from 10 to 10% by weight, more preferably from 0.05 to 8% by weight, and particularly preferably from 0.05 to 5% by weight. If the content of the alkylphenol-based surfactant is too small, the developability tends to be insufficient. If the content is too large, the entire photoresist tends to peel off from the substrate, and selective removal tends to be impossible.

As the alkylphenol-based surfactant, a compound represented by the aforementioned general formula (1) is preferable. In the general formula (1), R ¹ is not particularly limited as long as it is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, whether linear or branched, and among them, an alkyl group or alkylene having 3 to 14 carbon atoms is preferable. A group is preferable, an alkyl group or an alkylene group having 3 to 11 carbon atoms is more preferable, and an alkyl group or an alkylene group having 3 to 9 carbon atoms is particularly preferable. If the aliphatic hydrocarbon group has more than 19 carbon atoms, the solubility in water tends to be poor and the developability tends to be poor. Further, n is preferably an integer of 1 to 50, more preferably an integer of 5 to 40, and particularly preferably an integer of 10 to 35. If n exceeds 50, the foaming property tends to be high, and spray development tends to be difficult.

The compound represented by the general formula (1) includes
Examples thereof include polyoxyethylene cumyl phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether. Among the polyoxyethylene nonylphenyl ethers, those in which n in the general formula (1) is 28 to 32 are preferable. In addition,
In the general formula (1), when t = 0, R ¹ is an alkyl group, and when t = 1, R ¹ is an alkylene group.

The content of the alkyl ether surfactant is preferably from 0.005 to 20% by weight, more preferably from 0.01 to 20% by weight, based on the total amount of the developer. It is more preferably from 0.05 to 10% by weight, more preferably from 0.05 to 8% by weight, particularly preferably from 0.05 to 5% by weight. If the content of the alkyl ether-based surfactant is too small, the developability tends to be insufficient. If the content is too large, the entire photoresist tends to peel off from the substrate, and selective removal tends to be impossible.

Examples of the alkyl ether surfactant include:
The compound represented by the general formula (2) is preferable. In the general formula (2), R ² is not particularly limited as long as it is a linear or branched alkyl group as long as it is an alkyl group having 1 to 100 carbon atoms.
Among them, an alkyl group having 1 to 50 carbon atoms is preferable, an alkyl group having 1 to 40 carbon atoms is more preferable, and an alkyl group having 4 to 30 carbon atoms.
Is particularly preferable, and an alkyl group having 11 or 12 carbon atoms is most preferable. If the carbon number of the alkyl group exceeds 100, the solubility in water tends to be poor, and the developability tends to be poor. Further, n is preferably an integer of 1 to 50, more preferably an integer of 5 to 40, and particularly preferably an integer of 8 to 35. When n exceeds 50, the foaming property tends to increase,
In addition, spray development tends to be difficult.

The developer of the present invention contains anionic dispersants such as polycarboxylic acid type polymer surfactants and polysulfonic acid type polymer surfactants, and nonionic type dispersants such as polyoxyethylene / polyoxypropylene block polymers. Surfactants other than the above, such as agents, may be dissolved and contained. The content is preferably 100% by weight or less, particularly preferably 50% by weight or less, based on the total amount of the alkylphenol-based surfactant and the alkyl ether-based surfactant.

The colored image forming material used in the present invention comprises:
There is no particular limitation as long as it has photosensitivity and can be alkali-developed, but preferably contains a resin, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator.

As the resin used in the colored image forming material used in the present invention, a resin which does not hinder photosensitivity and has pigment dispersibility, film forming property and alkali developability when used as the colored image forming material. There are no particular restrictions. As such a resin, a cellulosic resin such as carboxymethylhydroxyethylcellulose and hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and the like can be used, and (meth) acrylic acid (means acrylic acid and methacrylic acid. The same.), Carboxyl group-containing polymerizable monomers such as itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride, monoalkyl citraconic acid, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, (Meth) acrylates such as butyl methacrylate, methyl acrylate, propyl acrylate, and butyl acrylate, styrene, styrene derivatives, and other polymerizable monomers And a copolymer of particularly preferred.

The monoalkyl maleate is preferably an alkyl group having 1 to 12 carbon atoms in the alkyl group, such as monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, isopropyl maleate and mono-maleate. n-butyl, maleic mono-n
-Hexyl, mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like.

Examples of the monoalkyl citraconic acid ester include monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, mono-isopropyl citraconic acid, and mono-n-citraconic acid.
Examples thereof include butyl, mono-n-hexyl citraconic acid, mono-n-octyl citraconic acid, mono-2-ethylhexyl citraconic acid, mono-n-nonyl citraconic acid, and mono-n-dodecyl citraconic acid.

As the styrene derivative, for example, α-
Methylstyrene, m- or p-methoxystyrene, p-
Hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like can be mentioned.

As the above-mentioned resin, a resin having a photopolymerizable unsaturated bond may be used for the purpose of improving photosensitivity and the like. Preferred examples of such a resin include oxirane rings such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and monoalkyl glycidyl ether itaconate in a high acid value carboxyl group-containing resin. And a compound having one ethylenically unsaturated bond, allyl alcohol, 2-buten-4-ol, furfuryl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate,
A resin obtained by reacting a compound having one ethylenically unsaturated bond (unsaturated alcohol) such as hydroxyethyl methacrylate or N-methylol acrylamide, or a carboxyl group-containing resin having a hydroxyl group is reacted with a free isocyanate group-containing unsaturated compound. Resin reacted, resin obtained by reacting polybasic anhydride with addition reaction product of epoxy resin and unsaturated carboxylic acid, addition reaction of conjugated diene polymer or conjugated diene copolymer with unsaturated dicarboxylic anhydride And a resin in which a hydroxyl-containing polymerizable monomer is reacted. The unsaturated equivalent of these resins is from 600 to 30
It is preferably in the range of 00, more preferably in the range of 800 to 2000. When the unsaturated equivalent is too small, the pigment tends to be partially cured when dispersing the pigment in the resin during preparation of the photosensitive material, and when the unsaturated equivalent is too large, the effect of improving the photosensitivity due to the introduction of the unsaturated group decreases. Tend to. In addition, the unsaturated equivalent here means the molecular weight of the resin per one unsaturated bond.

The above resin has an acid value of 20 from the viewpoint that the colored image forming material has alkali developability after exposure.
It is preferably within the range of 300 to 300, and more preferably 40 to 2
It is preferably in the range of 00, and particularly preferably in the range of 60 to 170. If the acid value is less than 20, alkali developability tends to decrease, and if it exceeds 300, the shape of the image pattern after alkali development tends to be unclear.

The weight average molecular weight of the resin is 1,
It is preferably in the range of 500 to 200,000, more preferably in the range of 5,000 to 100,000, and particularly preferably in the range of 10,000 to 50,000. Weight average molecular weight is 1,500
When the amount is less than 200, the dispersion stability of the pigment tends to decrease, and when the amount exceeds 200,000, the viscosity becomes high when the composition is made into a photosensitive liquid, and the coating property particularly at the time of spin coating tends to decrease.

Here, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

As the resin, those having an acid value of from 20 to 300 and a weight average molecular weight of from 1,500 to 200,000 are preferable, and such resins are particularly represented by the following general formulas (3) and (3). A resin having the repeating unit represented by 4) in the general formula (3) / general formula (4) at a ratio of 1/1 to 5/1 (molar ratio) is preferable in terms of pigment dispersibility and photosensitivity.

[0038]

Embedded image (Wherein, R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ and R ⁶ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. )

[0039]

Embedded image (Wherein, in the formula, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁹ represents a hydrogen atom or a group having 1 to 12 carbon atoms. Represents an alkyl group.) In addition, (i) in the general formula (4),
R ⁷ is a group having a photoreactive unsaturated bond, R ⁸ is a hydrogen atom,
A resin having a repeating unit wherein R ⁹ is a hydrogen atom, (i.
i) In the general formula (4), R ⁷ is a group having a photoreactive unsaturated bond, R ⁸ is a hydrogen atom or a group having a photoreactive unsaturated bond, and a resin having a repeating unit in which R ⁹ is a hydrogen atom. (Iii) In the general formula (4), R ⁷ represents a group having a photoreactive unsaturated bond or a hydrogen atom, R ⁸ represents a group having a photoreactive unsaturated bond, and a repeating unit wherein R ⁹ represents a hydrogen atom. Or (iv) in the general formula (4), R ⁷ and R ⁸ are each independently a hydrogen atom or a group having a photoreactive unsaturated bond, and at least one of them is a photoreactive unsaturated bond. And a resin having a repeating unit in which R ⁹ is an alkyl group having 1 to 12 carbon atoms.

As a method for producing a resin having a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4), for example, the repeating unit represented by the general formula (3) As a precursor of the resin having a repeating unit represented by the general formula (4), unsaturated alcohols (allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol,
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, etc.) by esterification reaction, a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4). Compounds each having one oxirane ring and one ethylenically unsaturated bond (glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate) And the like) to carry out an addition reaction.

As the precursor of the resin having the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4), styrene or a derivative thereof, maleic anhydride or monoalkyl maleate is used. (Half ester of maleic acid).

Examples of the styrene derivative include α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like.

Examples of the monoalkyl maleate include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate, mono-n-butyl maleate, mono-n-hexyl maleate, Mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like can be mentioned.

Examples of the monoalkyl citraconic acid ester include monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, mono-isopropyl citraconic acid, mono-n-butyl citraconic acid and mono-n-hexyl citraconic acid. And mono-n-nonyl citraconic acid, mono-n-dodecyl citraconic acid, and the like.

As the resin used in the colored image forming material used in the present invention, a resin having a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4) is used. When used, other resins may be used in combination. As the other resin, a resin other than the resin having the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) among the resins described above is used. Resin, epoxy resin,
Urethane resin, melamine resin and the like may be used. The other resin is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the resin.

The amount of the resin used in the colored image forming material used in the present invention is preferably 10 to 85% by weight, preferably 20 to 6% by weight, based on the total amount of the colored image forming material.
More preferably, it is 0% by weight.

Next, the pigment used in the colored image forming material will be described. As the pigment of the colored image forming material in the present invention, there are an inorganic pigment and an organic pigment, and any of them can be used. However, black carbon black (inorganic pigment) and an organic pigment are preferable from the viewpoint of abundant color tone.

Examples of the organic pigment include azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine-azomethine, and isoindolinone.

When the colored image forming material of the present invention is applied to a color filter, a pigment system suitable for red, green, blue and black colored images is used.

For a red colored image, a single red pigment system may be used, or a yellow pigment system or an orange pigment system may be mixed with a red pigment system for toning. Examples of red pigments include, for example, Pigment Red 9, 123, 155, 168, 177, 180, 21 in the color index name.
7, 220, 224, and 254. Also,
As the yellow pigments, for example, Pigment Yellow 17, 20, 24, 83, 93, 1
09, 110, 117, 125, 128, 129, 13
8, 139, 147, 150, 154 and the like. Examples of orange pigments include Pigment Orange 43, 48, and 71 under the color index name. These red, yellow or orange pigments can be used as a mixture of two or more kinds. When a mixture of a red pigment system and a yellow pigment system or an orange pigment system is used,
It is preferable to use the yellow pigment system or the orange pigment system in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the red pigment system and the yellow pigment system or the orange pigment system.

For a green colored image, a single green pigment system may be used, or a yellow pigment system may be mixed with a green pigment system for toning. Examples of the green pigment include Pigment Green 7, 36, and 37 under the name of color index. Further, as a yellow pigment, for example, Pigment Yellow 17, 20, by color index name,
24, 83, 93, 109, 110, 117, 125,
128, 129, 138, 139, 147, 150, 1
54 and the like. These green and yellow pigments can be used as a mixture of two or more kinds. When a green pigment and a yellow pigment are used in combination, it is preferable to use the yellow pigment at 50 parts by weight or less based on 100 parts by weight of the total of the green pigment and the yellow pigment.

For 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 blue pigments include, for example, Pigment Blue 15, 15: 3, 1
5: 4, 15: 6, 22, 60 and the like. Also,
Examples of purple pigments include, for example, Pigment Violet 19, 23, 29, 37, 50 under the color index name.
And the like. These blue and violet pigments can be used as a mixture of two or more kinds. When a mixture of a blue pigment and a violet pigment is used, it is preferable to use 50 parts by weight or less of the violet pigment based on 100 parts by weight of the total of the blue pigment and the violet pigment.

For the black colored image, for example, black pigments such as carbon black, graphite, titanium carbon, black iron oxide, and manganese dioxide are used.

The amount of the pigment used in the colored image forming material used in the present invention is the total amount of the colored image forming material comprising a resin, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator. Is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 15 to 30% by weight. If the amount is less than 5% by weight, the color density of the image tends to decrease, and if it exceeds 50% by weight, the light sensitivity tends to decrease.

Among the monomers having one or more photopolymerizable unsaturated bonds in the molecule used in the colored image forming material, the monomer having one photopolymerizable unsaturated bond in the molecule is methyl methacrylate. , Butyl methacrylate, alkyl methacrylates such as 2-ethylhexyl methacrylate, alkyl acrylates such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, aralkyl methacrylates such as benzyl methacrylate, aralkyl acrylates such as benzyl acrylate, and alkoxyalkyl methacrylates such as butoxyethyl methacrylate. , Alkoxyalkyl acrylates such as butoxyethyl acrylate, aminoalkyl methacrylates such as N, N-dimethylaminoethyl methacrylate, N Aminoalkyl acrylates such as N- dimethylaminoethyl acrylate, methacrylic acid esters of (diethylene glycol ethyl ether),
Methacrylic acid esters of (polyalkylene glycol alkyl ether) such as methacrylic acid esters of (triethylene glycol butyl ether) and methacrylic acid esters of (dipropylene glycol methyl ether);
Acrylic ester of (diethylene glycol ethyl ether), (triethylene glycol butyl ether)
(Polyalkylene glycol alkyl ether) such as acrylic acid ester of (dipropylene glycol methyl ether), (polyalkylene glycol aryl ether) such as methacrylic acid ester of (hexaethylene glycol phenyl ether) Acrylates of (polyalkylene glycol aryl ethers) such as acrylates of (hexaethylene glycol phenyl ether), dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate, methoxylated cyclo Decatriene methacrylate, isobornyl acrylate, methoxylated cyclodecatriene acrylate, glycerol methacrylate, glycero Le acrylate, fluorinated alkyl methacrylates such as hepta decafluoro decyl methacrylate, fluorinated alkyl acrylates such as hept decafluoro decyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate.

Among monomers having one or more photopolymerizable unsaturated bonds in the molecule, two or more photopolymerizable unsaturated bonds in the molecule are used.
As the monomer having at least one, 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 trimethacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pen Methacrylate, 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, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol Hexaacrylate, dipentaerythritol pentaacrylate and the like can be mentioned.

The monomer having two or more photopolymerizable unsaturated bonds in a molecule used in the colored image forming material may further include a compound represented by formula (a):

[0058]

Embedded image (Wherein, R represents an ethylene group or a propylene group, a and b each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of bisphenol A represented by the general formula ( b)

[0059]

Embedded image (Wherein, c and d each independently represent 1 to 10
Indicates an integer. Epichlorohydrin-modified bisphenol A and addition ester of acrylic acid represented by
Bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, general formula (c)

[0060]

Embedded image (Wherein, R represents an ethylene group or a propylene group, e and f each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula ( d)

[0061]

Embedded image (Where g and h are each independently 1 to 10
Indicates an integer. Phthalic acid-modified epichlorohydrin and acrylic acid addition ester, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol diacrylate, represented by formula (e):

[0062]

Embedded image (Where i and j are independently 1 to 20
Indicates an integer. ), An addition esterified product of acrylic acid and an epichlorohydrin modified product of 1,6-hexanediol (having two acrylic groups in one molecule), trimethylolpropane triacrylate, pentaerythritol triacrylate, and a compound represented by the general formula (f) )

[0063]

Embedded image (Wherein, R represents an ethylene group or a propylene group, and three k's each independently represent an integer of 1 to 20.) A triacrylate of an alkyne oxide adduct of phosphoric acid represented by the general formula: (G)

[0064]

Embedded image (Wherein, R represents an ethylene group or a propylene group, and p, q and r each independently represent an integer of 1 to 20). A triacrylate of an alkylene oxide adduct of trimethylolpropane represented by Tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like can be mentioned. These monomers can be used alone or in combination of two or more.

The compounding amount of the monomer having one or more photopolymerizable unsaturated bonds in the molecule of the colored image forming material in the present invention is determined by the amount of the resin, the pigment and the monomer having one or more photopolymerizable unsaturated bonds in the molecule. And 2 to 50% by weight, more preferably 5 to 40% by weight, and more preferably 10 to 40% by weight based on the total amount of the colored image forming material comprising
It is particularly preferred to be 30% by weight. This amount is
If it is less than 2% by weight, the light sensitivity tends to be low,
If it exceeds 50% by weight, the dispersion stability of the pigment tends to decrease.

The photoinitiator of the colored image forming material in the present invention is not particularly limited, and benzophenone, N,
N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α- Hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, t-butylanthraquinone, 1-chloroanthraquinone , 2, 3
-Dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-
Examples thereof include benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, and a triazine-based photoinitiator. These photoinitiators can be used alone or in combination of two or more.

The compounding amount of the photoinitiator of the colored image forming material used in the present invention may be a resin, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule, and a colored image forming material comprising a photoinitiator. 0.01 to 100 parts by weight of the total amount
The amount is preferably from 20 to 20 parts by weight, more preferably from 2 to 15 parts by weight, and particularly preferably from 5 to 10 parts by weight. If the amount is less than 0.01 part by weight, the photosensitivity tends to decrease, and if it exceeds 20 parts by weight, the adhesiveness tends to decrease.

The colored image-forming material used in the present invention contains, in addition to essential components such as a resin, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator,
Thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol for suppressing dark reaction, and silane coupling agents (vinyl group, epoxy group,
An amino group, a mercapto group, etc.), a titanate coupling agent (isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.), a surfactant (fluorine-based, Various additives such as silicon-based and hydrocarbon-based), ultraviolet absorbers, and antioxidants can be used as needed.

The colored image forming material used in the present invention includes:
A photosensitive liquid is formed by adding an appropriate organic solvent, and the photosensitive liquid is formed as a film on a substrate by using a spin coater or the like. Thereafter, exposure and development are performed to obtain a target image pattern.

Next, a method of using the colored image forming material used in the present invention as a photosensitive liquid will be described.

First, it is necessary to disperse the pigment used in the colored image forming material. As this method, usually, a resin and a pigment are mixed with an organic solvent, and the mixture is kneaded using a dispersing / kneading device such as an ultrasonic disperser, a three-roll, a ball mill, a sand mill, a bead mill, a homogenizer, a kneader, and a nanomizer. There is a way to do that.

The organic solvent used at this time is not particularly restricted but includes, for example, ketones, cellosolves, alcohols and aromatics. Specifically, acetone, methyl ethyl ketone, cyclohexanone, methyl cellosolve (diethylene glycol dimethyl ether),
Ethyl cellosolve, butyl cellosolve, 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, triethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutanol , 3-methyl-3-methoxybutyl acetate, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, Organic solvents such as xylene and ethyl acetate are exemplified. These can be used alone or in combination of two or more.

At the time of pigment dispersion, anionic pigment dispersants such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and pigments such as nonionic pigment dispersants such as polyoxyethylene / polyoxypropylene block polymers. Dispersant, anthraquinone type, perylene type, phthalocyanine type, carboxyl group to organic dyes such as quinacridone type,
It is preferable to add a derivative of an organic dye into which a substituent such as a sulfonate group, a carboxylic acid amide group, or a hydroxyl group is introduced, since 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 weight or less based on 100 parts by weight of the pigment.

The monomer having one or more photopolymerizable unsaturated bonds in the molecule and the photoinitiator may be added at the time of pigment dispersion or after the pigment dispersion.

The entire amount of the resin may be used together with the pigment at the time of dispersion, or a part of the resin may be added after the dispersion. However, at the time of dispersion, it is preferable to use at least 20 parts by weight of the resin with respect to 100 parts by weight of the pigment. If it is less than 20 parts by weight, the dispersion stability of the pigment tends to decrease.

Similarly, the organic solvent may be used in its entirety at the time of dispersion of the pigment, or a part of the organic solvent may be added after the dispersion. However, it is preferable to use at least 100 parts by weight of the organic solvent at the time of dispersion with respect to 100 parts by weight of the total amount of the pigment and the resin at the time of dispersion. If it is less than 100 parts by weight, the viscosity at the time of dispersion is too high, and dispersion may be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a bead mill or the like.

The total amount of the organic solvent, including the resin, the pigment, the monomer having at least one photopolymerizable unsaturated bond in the molecule, and the photoinitiator in the photosensitive solution is in the range of 5 to 40% by weight. It is preferable to use it.

Examples of the method of applying such a photosensitive liquid to a substrate include, for example, roll coater coating, spin coater coating, spray coating, white coater coating, dip coater coating, curtain flow coater coating, wire bar coater coating, and gravure coater coating. And air knife coater application. The substrate used at this time is selected depending on the application, for example, white plate glass, blue plate glass,
Transparent glass substrate such as silica-coated blue plate glass, polyester resin, polycarbonate resin, acrylic resin, synthetic resin sheet such as vinyl chloride resin, film or substrate,
Examples include a metal substrate such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate, other ceramic substrates, and a semiconductor substrate having a photoelectric conversion element.

After the application, the temperature is usually 1 to 50 ° C. to 130 ° C.
The thickness of the film containing the colored image forming material formed on the substrate surface in this manner is appropriately determined depending on the application, but is usually 0.1 to 300 μm.
m. When used for a color filter, it is usually used in the range of 0.2 to 5 μm.

Next, a method for forming an image pattern will be described.

The film on the substrate obtained by the above method is irradiated with actinic rays imagewise to cure the film in the exposed portion. Further, an oxygen barrier film such as polyvinyl alcohol having a thickness of 0.5 to
It may be formed with a thickness of 30 μm and exposed from above.

As a light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a visible light laser and the like are suitable. Using these light sources, actinic rays are irradiated imagewise by pattern exposure through a photomask, direct drawing by scanning, or the like.

Subsequently, a developing step is performed using the developing solution of the present invention. That is, the unexposed portions are removed by spraying a developer or dipping in a developer to obtain a colored image pattern of a cured film corresponding to an image.

After development, the colored image pattern is further exposed to light of 0.5 to 5 mJ / cm ² using a high-pressure mercury lamp or the like, or post-heated at a temperature of 60 to 200 ° C. for 1 to 60 minutes. Then, the image pattern becomes stronger, which is preferable.

As an example of the production of a color filter used for a liquid crystal display device, the above-described method is repeated by using a colored image forming material on a glass substrate,
After forming a colored image of red, green, blue, etc., a method of forming a black colored image as a black matrix in the gap between the colored pixels, or after forming a black matrix by chrome evaporation or black colored image first , Red as above,
There is a method of forming a color filter in which colored pixels such as green and blue are formed.

[0086]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited by these examples. (1) Resin used: 50 mol% of styrene-20 mol% of maleic acid monopropyl ester-maleic acid derivative 3
A copolymer consisting of 0 mol%, having a weight average molecular weight of 11,000 and an acid value of 65 (hereinafter referred to as copolymer A). (2) The repeating unit based on the maleic acid derivative has the following structure: is there.

[0087]

Embedded image Production Example 1 of Photosensitive Liquid (Production Example of Photosensitive Liquid for Forming Black Colored Image) 10 g of copolymer A as a resin, 38 g of carbon black as a pigment, and 200 g of diethylene glycol dimethyl ether were kneaded for 2 hours using a bead mill to prepare a colored resin composition. Obtained.

This colored resin composition, 32 g of trimethylolpropane triacrylate as a monomer, 12 g of benzophenone and 4 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator, and diethylene glycol dimethyl ether 20 as an organic solvent
0 g was added and mixed to obtain a black colored image forming photosensitive liquid.

Production Example 2 of Photosensitive Liquid (Production Example of Photosensitive Liquid for Forming Red Colored Image) 30 g of copolymer A as a resin and C.I. I. Pigment Red 177 and C.I. I. Pigment Yellow 139 and 200 g of diethylene glycol dimethyl ether were kneaded for 2 hours using a Bees mill to obtain a colored resin composition.

This colored resin composition, 32 g of pentaerythritol tetraacrylate as a monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator and diethylene glycol dimethyl ether 200 as an organic solvent
g was added and mixed to obtain a red colored image forming photosensitive liquid.

Production Example 3 of Photosensitive Liquid (Production Example of Photosensitive Liquid for Forming a Green Colored Image) 40 g of a copolymer as a resin and C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 83 was used in the same manner as in Production Example 2 of the photosensitive solution except that 5 g of Pigment Yellow 83 was used, to obtain a green colored photosensitive solution for forming an image.

Production Example 4 of Photosensitive Liquid (Production Example of Photosensitive Liquid for Forming Blue Colored Image) 40 g of copolymer A as a resin and C.I. I. Pigment Blue 15: 6 and C.I. I. Pigment Violet 23 was used in the same manner as in Production Example 2 of the photosensitive liquid except that 4 g of Pigment Violet 23 was used to obtain a blue colored photosensitive liquid for image formation.

Example 1 The photosensitive liquid for forming a black colored image obtained in Production Example 1 of a photosensitive liquid was applied on a glass substrate (Corning Co., trade name: 7059) by a spin coater method, and further heated at 110 ° C. for 5 minutes. Drying was performed to form a film having a thickness of 1.0 μm.

The resulting film was exposed imagewise at 700 mJ / cm ^{2 with} a super-high pressure mercury lamp through a negative mask, and then polyoxyethylene cumyl phenyl ether (in the following formula (5), n is 12) Development was carried out with an aqueous solution containing 0.15% by weight, 0.15% by weight of polyoxyethylene lauryl ether (where n in the general formula (2) is 10) and 0.3% by weight of potassium hydroxide.
Table 1 shows the evaluation results of the development time, pixel resolution, and development residue at that time.

[0095]

Embedded image Example 2 The photosensitive liquid for forming a red colored image obtained in Production Example 2 of the photosensitive liquid was applied on a glass substrate in the same manner as in Example 1, and dried.
A film having a thickness of 2.0 μm was formed.

The obtained film was exposed to an image of 100 mJ / cm ² by means of an ultra-high pressure mercury lamp through a negative mask, and then exposed to polyoxyethylene cumyl phenyl ether (in the formula (5), n = 12). .15% by weight of polyoxyethylene lauryl ether (n in the general formula (2)
Was developed with an aqueous solution containing 0.15% by weight and 0.3% by weight of potassium hydroxide. Table 1 shows the evaluation results of the development time, pixel resolution and development residue at that time.
It was shown to.

Example 3 The green colored image forming photosensitive liquid obtained in Preparation 3 of the photosensitive liquid was applied to a glass substrate in the same manner as in Example 1, and dried.
A film having a thickness of 2.0 μm was formed.

The obtained film was exposed by the same method and under the same conditions as in Example 2, and then exposed to polyoxyethylene cumyl phenyl ether (in the formula (5), wherein n is 12).
The development was carried out using an aqueous solution containing 0.15% by weight of polyoxyethylene lauryl ether (wherein n is 10 in the general formula (2)) and 0.3% by weight of potassium hydroxide.
Table 1 shows the evaluation results of the development time, pixel resolution, and development residue at that time.

Example 4 The photosensitive liquid for forming a blue colored image obtained in Production Example 4 of the photosensitive liquid was applied onto a glass substrate in the same manner as in Example 1, and dried.
A film having a thickness of 2.0 μm was formed.

The obtained film was exposed to light in the same manner and under the same conditions as in Example 2. Then, polyoxyethylene cumylphenyl ether (in the formula (5), n is 12)
The development was carried out using an aqueous solution containing 0.15% by weight of polyoxyethylene lauryl ether (wherein n is 10 in the general formula (2)) and 0.3% by weight of potassium hydroxide.
Table 1 shows the evaluation results of the development time, pixel resolution, and development residue at that time.

Example 5 A red image pattern was formed on a glass substrate having a black matrix formed of chromium in the same manner and under the same conditions as in Example 2, and then heated at 180 ° C. for 10 minutes. Next, a green image pattern was formed next to the red image pattern using the substrate under the same method and conditions as in Example 3, and then heated at 180 ° C. for 10 minutes. Next, using this substrate, a blue image pattern was formed next to the green image pattern under the same method and conditions as in Example 4, and then heating was performed at 200 ° C. for 10 minutes. As described above, a color filter in which one pixel was arranged in a mosaic shape of three colors of red, green, and blue of 30 μm × 100 μm was produced.

Example 6 The same method and under the same conditions as in Example 1 were applied to a glass substrate with a width 2
0 μm black image pattern (black matrix)
Was formed and heated at 205 ° C. for 20 minutes. Next, pixels are formed in the order of red, green, and blue in the same manner as in Example 5, and one pixel is a 30 μm × 100 μm mosaic-shaped color filter composed of three colors of red, green, and blue. Produced.

Comparative Example 1 Using the same photosensitive solution as in Example 1 except that an aqueous solution containing 0.3% by weight of sodium hydroxide was used as a developing solution, a black solution was obtained in the same manner and under the same conditions as in Example 1. An image was formed. Table 1 shows the evaluation results of the development time, pixel resolution, and development residue at that time.

Comparative Example 2 Except that an aqueous solution containing 0.15% by weight of polyoxyethylene cumylphenyl ether (in the formula (5), n is 12) and 0.3% by weight of potassium hydroxide was used as a developer. A black image was formed using the same photosensitive liquid as in Example 1 and using the same method and conditions as in Example 1. Table 1 shows the evaluation results of the development time, pixel resolution, and development residue at that time.

Comparative Example 3 A developer was prepared using an aqueous solution containing 0.15% by weight of polyoxyethylene lauryl ether (in the general formula (2), n is 10) and 0.3% by weight of potassium hydroxide. Using the same photosensitive liquid as in Example 1, a black image was formed under the same method and conditions as in Example 1. Table 1 shows the evaluation results of the development time, pixel resolution, and development residue at that time.

[0106]

[Table 1] 1) Spray development (spray pressure: 0.1 kg / mm ² )
2) A: No development residue was observed in the unexposed area.

X: Development residue increased in unexposed areas.

From Table 1, it can be seen that the development time using the developer according to the present invention (Examples 1 to 4) is shorter than that using the developer outside the scope of the present invention (Comparative Examples 1 to 3). Can be shortened. In addition, the resolution of the image patterns obtained in Examples 1 to 4 was higher than Comparative Examples 1 to 3, and no development residue was observed in the unexposed portions after development.

As described above, the color filters (Examples 5 and 6) prepared by using a developing solution having an excellent developing property, which are not heretofore known, have depolarizing properties of 700 or more and have excellent optical properties, and are effective as image display elements. Was confirmed.

[0110]

The developing solution of the present invention improves the developing time, the resolution and the development residue, which are problems of the developing solution of the photosensitive material in which the pigment is dispersed.

According to the method for producing a colored image of the present invention, a colored image having excellent resolution, little development residue, and a dispersed pigment can be formed.

According to the method for producing a color filter of the present invention, a high-quality color filter suitable for an image display device can be produced.

Continued on the front page (72) Inventor Koji Yamazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Inside the Goi Plant of Hitachi Chemical Co., Ltd. (72) Inventor Seigo Yokochi 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Inside the factory (72) Inventor Shinya Kato 14 Goi south coast, Ichihara city, Chiba prefecture Hitachi Chemical Co., Ltd.Goi factory (72) Inventor Liu Junlin 14 Goi south coast, Ichihara city, Chiba prefecture Hitachi chemical industry Goi factory F term (reference) 2H025 AA02 AA04 AB13 AD01 BC31 CB42 CC04 2H048 AA05 AA09 BA17 BA24 2H096 AA22 GA09 GA11

Claims (8)

[Claims] 1. A developer comprising a basic compound, an alkylphenol-based surfactant and an alkylether-based surfactant. 2. The compound showing basicity is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
The developer according to claim 1, wherein the developer is at least one inorganic alkali compound selected from the group consisting of sodium metasilicate and potassium metasilicate. 3. An alkylphenol-based surfactant represented by the following general formula (1): ## STR1 ## (Wherein, R ¹ represents an aliphatic hydrocarbon group having 1 to 19 carbon atoms, t is 0 or 1, and n is an integer of 1 to 50). Or the developer according to 2. 4. An alkyl ether-based surfactant represented by the following general formula (2): (Wherein, R ² represents an alkyl group having 1 to 100 carbon atoms;
m is an integer of 1 to 50. The developer according to claim 1, 2 or 3, which is a compound represented by the formula: 5. The method according to claim 1, wherein the concentration of the compound showing basicity is from 0.01 to 0.01.
The concentration of the alkylphenol-based surfactant is 0.01 to 20% by weight, and the concentration of the alkylether-based surfactant is 0.01 to 20% by weight.
The developer according to any one of the above. 6. A method for producing a colored image, which comprises laminating a layer of a photosensitive colored image-forming material which is alkali-developable and photosensitive on a substrate, and exposing and developing the colored image, comprising: Item 5. A method for producing a colored image, comprising using the developer according to any one of Items 1 to 4. 7. An alkali-developable, photosensitive colored image-forming material containing a resin having an acid value of 20 to 300, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator. 7. The method for producing a colored image according to claim 6, wherein 8. A method for producing a color filter, comprising producing a plurality of colored images on the same substrate by the method for producing a colored image according to claim 6.