JPH1172907A - Color image forming photosensitive solution and manufacture of color filter by using the same and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color image forming photosensitive solution capable of enlarging process latitude, remarkably reducing development remainder, and attaining high resolution by incorporating a specified compound. SOLUTION: This color image forming photosensitive solution comprises a resin, a pigment, a monomer having a photopolymerizable unsaturated bond, a photopolymerization initiator, an organic solvent, and the compound represented by the formula in which R<1> is an H atom or a 1-22C alkyl or 6-14C aryl group; each of R<2> -R<4> is independently, a 2-4C alkylene group; and each of (p)-(r) is an integer of 0-200 and p+q+r>=1. The compound of the formula is embodied by polyethylene glycol, polypropylene glycol, and the like, and it is used, preferably, in an amount of 0.001-5 pts.wt. to 100 pts.wt. of the total components be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive solution for forming a colored image, a method for producing a color filter using the same, and 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 producing this color filter, a method of patterning a dyeable resin, for example, natural gelatin or casein, and then dyeing the pattern with a dye to obtain pixels has been used. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials. Therefore, recently, a method of using a photosensitive material in which a pigment is dispersed has been attracting attention for the purpose of improving heat resistance and light resistance, and many studies have been made. According to this method, it is known that the manufacturing method is simplified, and the obtained color filter is stable and has a long life. However, the conventional material for a color filter has a problem that the process margin is narrow, and if it is out of the optimum condition, a development residue remains on the substrate after development, and the resolution is deteriorated.

[0003]

SUMMARY OF THE INVENTION The first and second aspects of the present invention provide a photosensitive solution for forming a colored image which has a wide process latitude, can significantly reduce the undeveloped development, and can achieve high resolution. A third aspect of the present invention provides a photosensitive solution for forming a colored image which has the effects of the first aspect of the present invention, and further has excellent light sensitivity, heat resistance, and the like. Claim 4
The inventions described in (5) and (5) provide a process for producing a color filter which has a wide process latitude, can reduce development residue, and can achieve high resolution. The invention according to claim 6 provides a high-precision and high-quality color filter.

[0004]

The present invention provides (a) a resin,
(B) a pigment, (c) a monomer having a photopolymerizable unsaturated bond, (d) a photopolymerization initiator, (e) an organic solvent, and (f) the following general formula (I)

Embedded image (Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aryl group having 1 to 14 carbon atoms, and R ² , R ³ and R ⁴ each independently represent an alkylene having 2 to 6 carbon atoms. Represents a group, different from R ² and R ³ , different from R ³ and R ⁴ , p, q
And r are each independently an integer from 0 to 200, and p + q
+ R ≧ 1) is contained in the photosensitive solution for forming a colored image.

Further, the present invention relates to (a) a resin having an acid value of 2
0-300, weight average molecular weight 1,500-200,0
The colored image forming photosensitive liquid is a resin of No. 00.

In the present invention, the resin (a) is a compound represented by the general formula (II):

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms), and a general formula (II
I)

Embedded image Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a group having a photoreactive unsaturated bond. The present invention relates to a photosensitive liquid for image formation.

Further, the present invention provides a method for forming a film by applying the photosensitive liquid for forming a colored image on a substrate and drying the coated liquid, irradiating actinic rays imagewise, curing the exposed portion with light, A color filter manufacturing method, wherein the step of developing is repeatedly performed for a plurality of different colors to form pixels. The present invention also relates to a method for producing the color filter, wherein the plurality of different colors are red, green, blue and black. The present invention also relates to a color filter manufactured by the method for manufacturing a color filter.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The resin (a) in the present invention is not particularly limited as long as it has a film-forming property, and known resins can be used. An acid value of 20 from the viewpoint of properties
Weight average molecular weight (measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve) of from 1,500 to 2,
00,000 resins are preferred. The acid value of this resin is 40
It is more preferably from 200 to 200, and more preferably from 60 to 150. Further, the weight average molecular weight of this resin is more preferably 5,000 to 100,000, and particularly preferably 10,000 to 50,000. Examples of such a resin include a copolymer of a polymerizable monomer having a carboxyl group such as acrylic acid, methacrylic acid, and itaconic acid with a polymerizable monomer such as acrylate, methacrylate, and styrene.

Further, a carboxyl group-containing resin having a photopolymerizable unsaturated bond as the resin (a) is also preferred from the viewpoint of photosensitivity.

Examples of the carboxyl group-containing resin having a photopolymerizable unsaturated bond include a resin obtained by reacting a carboxyl group-containing resin having a hydroxyl group with a free isocyanate group-containing unsaturated compound, and a resin obtained by reacting an epoxy resin with an unsaturated carboxylic acid. A resin obtained by reacting a polybasic acid anhydride with an addition reaction product, a resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene polymer or a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride, Glycidyl group-containing unsaturated compounds (glycidyl methacrylate,
Allyl glycidyl ether, etc.) and unsaturated alcohols (allyl alcohol, 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate), the following general formula (II)

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms) and the following general formula (III)

Embedded image (Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond), and the like. Above all, a resin having a repeating unit represented by the general formula (II) and a repeating unit represented by the general formula (III) is preferable from the viewpoint of heat resistance, dispersibility, and the like.

In view of having better heat resistance and dispersibility, the resin having the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III) has the general formula (II) The ratio m / n between the number m of repeating units represented by the formula and the number n of repeating units represented by the general formula (III)
Is preferably 1 to 5. The mode of presence of these repeating units in the resin is not particularly limited, and may be any of random, block, alternating, or a combination thereof.

As a method for producing a resin having a repeating unit represented by the above general formula (II) and a repeating unit represented by the general formula (III), for example, styrene or a derivative thereof is copolymerized with maleic anhydride. A resin (SM resin) obtained by reacting an alcohol with a monoalkyl ester (also referred to as a half ester) of a maleic acid portion, styrene or a derivative thereof and a monoalkyl maleate (half ester of maleic acid) (Hereinafter referred to as an alkyl group-added SM resin) obtained by copolymerizing an unsaturated alcohol (allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinna Mill alcohol, 2-hydroxy acrylate, 2-hydroxy methacrylate, N-methyl Method for producing Lumpur acrylamide) by esterification reaction, the alkyl group imparting SM resin, an oxirane ring and an ethylenically unsaturated bond of a compound having one each (glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, alpha-
Ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, etc.).

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 monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate,
Mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate, mono-n-hexyl maleate, mono-n-octyl maleate, mono-n-ethylhexyl maleate, mono-maleate
n-nonyl, mono-n-dodecyl maleate and the like.

The resin having a repeating unit represented by the general formula (II) and a repeating unit represented by the general formula (III) preferably has an unsaturated equivalent of 300 to 3,000. If the unsaturated equivalent is less than 300, it tends to be partially cured when dispersed with the pigment, and if it exceeds 3,000, the effect of improving photosensitivity tends to be reduced. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

In the present invention, the amount of the resin used as the component (a) is 10% or less.
The amount is preferably 10 to 85 parts by weight, more preferably 20 to 60 parts by weight, and more preferably 2 to 60 parts by weight with respect to 0 parts by weight.
It is particularly preferred that the amount be 5 to 50 parts by weight. If the amount is less than 10 parts by weight, the dispersion stability of the pigment tends to decrease, and if it exceeds 85 parts by weight, the viscosity when used as a photosensitive liquid tends to increase, and the coatability tends to decrease.

As the pigment of the component (b) in the present invention, there are inorganic pigments and organic pigments. However, except for black carbon black, graphite and the like, organic pigments are generally used due to their rich color tone. . Examples of the organic pigment include azo-based, phthalocyanine-based, indigo-based, anthraquinone-based, perylene-based, quinacridone-based, methine-azomethine-based, and isoindolinone-based.

When the colored image forming photosensitive liquid of the present invention is applied to a color filter, each pigment system suitable for a colored image such as red, green, blue and black is used. As a red colored image, a single red pigment system may be used, or a yellow pigment system may be mixed with a red pigment system to perform toning. As a red pigment, for example, C. in the color index name
I. Pigment Red 9, 123, 155, 168, 17
7, 180, 217, 220, 224 and the like.
Examples of yellow pigments include, for example, CI Pigment Yellow 20, 24, 83, 93,
109, 110, 117, 125, 139, 147, 1
54 and the like. These red pigment systems and yellow pigment systems may be used as a mixture of two or more types. When a mixture of a red pigment system and a yellow pigment system is used, the yellow pigment system 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 red pigment system and the yellow pigment system. .

As the green colored image, a single green pigment system may be used, or the above-mentioned yellow pigment system may be mixed with a green pigment system to perform toning. Examples of green pigments include CI Pigment Green 7, 36, and 37 under the color index name. These green pigment system and yellow pigment system can be used as a mixture of two or more kinds. When the green pigment system and the yellow pigment system are mixed and used, the yellow pigment system 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 green pigment system and the yellow pigment system.

As the 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. As blue pigments, for example, CI Pigment Blue 15, 1
5: 3, 15: 4, 15: 6, 22, 60 and the like. Examples of purple pigments include, for example, CI Pigment Violet 19, 23, 29,
37, 50 and the like. These blue pigments 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, the violet pigment is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the blue pigment and the violet pigment.

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

In the present invention, the amount of the component (b) used is 10% of the total of the components (a), (b), (c) and (d).
The amount is preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight, and
It is particularly preferred that the amount is from 40 to 40 parts by weight. If the amount is less than 5 parts by weight, the color density of the image tends to be low,
If it exceeds 70 parts by weight, the light sensitivity tends to decrease.

As the monomer having a photopolymerizable unsaturated bond as the component (c) in the present invention, conventionally known monomers can be used. Examples thereof include methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxyethyl acrylate, and butoxytriacrylate. Ethylene glycol acrylate, dicyclopentanyl acrylate,
N, N-dimethylaminoethyl methacrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, isobornyl acrylate, methoxydipropylene glycol acrylate, methoxylated cyclodecatriene acrylate Phenoxyhexaethylene glycol acrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate,
1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, acrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate Examples include acrylates, acrylates such as tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate, and methacrylates corresponding thereto. These monomers are used alone or in combination of two or more.

The amount of the monomer (c) used in the present invention is 2 to 50 parts by weight based on 100 parts by weight of the total of the components (a), (b), (c) and (d). And more preferably 5 to 40 parts by weight,
It is particularly preferred that the amount be 0 to 30 parts by weight. If the amount of the monomer is less than 2 parts by weight, the photosensitivity tends to decrease, and if it exceeds 50 parts by weight, the dispersion stability of the pigment tends to decrease.

Examples of the photopolymerization initiator of the component (d) in the present invention include benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl and 2,2-diethoxy. Acetophenone, 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-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3
-Chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4
-Dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and the like. These photopolymerization initiators are used alone or in combination of two or more.

In the present invention, the amount of the photopolymerization initiator of the component (d) is 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (a), (b), (c) and (d). It is preferable to set it as weight part, it is more preferable that it is 2-15 weight part, and it is especially preferable that it is 5-10 weight part. 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 organic solvent as the component (e) in the present invention includes, for example, ketones, cellosolves, alcohols, aromatics and the like. Specifically, acetone,
Methyl ethyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, butyrocellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyrocellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, triethylene glycol Dimethyl 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 − 2-pyrrolidone, N- hydroxymethyl-2-pyrrolidone, methyl alcohol, ethyl alcohol, isopropyl alcohol, n- butyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, xylene, organic solvents such as ethyl acetate. These organic solvents are used alone or in combination of two or more.

The amount of the organic solvent used as the component (e) in the present invention depends on the amounts (a), (b),
It is preferable to use such that the total solid content including the components (c) and (d) is 5 to 40% by weight. When the amount is less than 5% by weight, it takes a long time to dry the coating film. When the amount exceeds 40% by weight, the viscosity of the photosensitive solution tends to be too high, and the coating property tends to be reduced.

In the general formula representing the component (f) in the present invention, examples of the aryl group include a phenyl group, a naphthyl group and an anthranyl group. These aryl groups are alkyl groups having 1 to 22 carbon atoms. It may be substituted with a styryl group or the like.

As the compound (f) of the present invention represented by the general formula (I), for example, polyethylene glycol (R ¹ is a hydrogen atom, R ² is an ethylene group, p is 2 to 100,
q and r are 0), polypropylene glycol (R ¹ is a hydrogen atom, R ² is a propylene group, p is 2 to 100, q and r are 0), methoxypolyethylene glycol (R ¹ is a methyl group, R ² is an ethylene group) , P is 2 to 100, q and r
Is 0), polyoxyethylene octyl phenyl ether (R ¹ is a phenyl group, R ² is an ethylene group, p is 2 to 30,
q and r are 0), polyoxyethylene nonylphenyl ether (R ¹ is a nonylphenyl group, R ² is an ethylene group, p
Are 2 to 30, q and r are 0), and polyoxyethylene dinonyl phenyl ether (R ¹ is a dinonyl phenyl group, R ²
Is an ethylene group, p is 2 to 30, q and r are 0), polyoxyethylene styryl phenyl ether (R ¹ is a styryl phenyl group, R ² is an ethylene group, p is 2 to 30, q and r are 0), Polyoxyethylene distyryl phenyl ether (R ¹ is a distyryl phenyl group, R ² is an ethylene group, p is 2 to 30, q and r are 0), polyoxyethylene lauryl ether (R ¹ is a lauryl group, R ² is Ethylene group, p is 4 to 30, q and r are 0), polyoxyethylene tridecyl ether (R ¹ is a tridecyl group, R ² is an ethylene group, p is 4 to 30, q and r are 0), polyoxyethylene polyoxyethylene oleyl ether (n = 4 to 30), polyoxyethylene cetyl ether (R ¹ is a cetyl group, R ² is an ethylene group, p is 4 to 30, q and r is 0), polyoxyethylene stearyl et Ether (R ¹ is stearyl group, R ² is an ethylene group, p is 4 to 20, q and r is 0), polyoxyethylene polyoxypropylene glycol (R ¹ is a hydrogen atom, R ² and R ⁴ is an ethylene group, R ³ is a propylene group,
p and r are 2 to 50, q is 4 to 50), polyoxyethylene polyoxypropylene nonyl ether (R ¹ is a nonyl group, R ² is an ethylene group, R ³ is a propylene group, p is 2 to 2)
50, q is 2 to 50, and r is 0). In addition,
The description in parentheses next to the compound name described above is represented by the general formula (I)
The correspondence with is shown.

The compound (f) is commercially available from Toho Chemical Industry Co., Ltd. under the trade name of Pepol, Nonal, Pegnol, etc. as a polyether type nonionic activator, and can also be used. .

In the present invention, (f) the compound represented by the general formula (I) is used in an amount of 0 to 100 parts by weight of the total amount of the components (a), (b), (c) and (d). .001-
It is preferably 5 parts by weight, more preferably 0.01 to 1 part by weight, and particularly preferably 0.05 to 0.5 part by weight. If this amount is less than 0.001 part by weight, there is no effect on the development residue and the improvement of the resolution.
When the amount is more than the weight part, applicability and adhesion tend to decrease. For the purpose of improving the development residue and resolution, in addition to the component (f),
A silicon-based surfactant or a fluorine-based surfactant may be used.

The photosensitive liquid for forming a colored image of the present invention suppresses a dark reaction in addition to the essential components (a), (b), (c), (d), (e) and (f). Polymerization inhibitors (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.), and silane coupling agents (vinyl group, epoxy group, amino group, mercapto group, etc.) for improving the adhesion to the substrate ), Titanate coupling agents (isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.), and surfactants (fluorine-based, silicon-based, hydrocarbon-based, etc.) for improving the smoothness of the film ) And other various additives such as an ultraviolet absorber and an antioxidant can be used as needed. Further, the photosensitive liquid for forming a colored image of the present invention contains a resin outside the range of the component (a) such as an acrylic resin, an epoxy resin, a urethane resin, and a melamine resin in 100 parts by weight of the resin (a). On the other hand, it can be used at 50 parts by weight or less. If the amount exceeds 50 parts by weight, the dispersion stability and photosensitivity of the pigment tend to decrease.

An example of the production of the colored image forming photosensitive liquid of the present invention will be described below. First, in order to disperse the pigment of the component (b), the resin of the component (a) and the pigment of the component (b) are mixed with the organic solvent of the component (e), and the mixture is subjected to an ultrasonic dispersing machine, a three-roll mill, This is performed using various dispersing and kneading apparatuses such as a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader. In the dispersing step, when a pigment dispersant or a derivative of an organic pigment in which a substituent (a carboxyl group, a sulfonate group, a carboxylic acid amide group, a hydroxyl group, etc.) is introduced into the organic pigment, and the like are added, the dispersibility and dispersibility of the pigment are increased. Good stability is preferable. These pigment dispersants and organic pigment derivatives are preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the pigment. Further, the components (c), (d) and (f) can be added at the time of pigment dispersion, and the components (c), (d) and (f) can be added after pigment dispersion.

The resin of the component (a) can be used in its entirety together with the pigment at the time of dispersion, or a part of the resin can be used after the dispersion. However, the resin is preferably used at least 20 parts by weight at the time of dispersion with respect to 100 parts by weight of the pigment. If the amount of the resin used is less than 20 parts by weight at the time of dispersion, the dispersion stability of the pigment tends to decrease. Similarly, the organic solvent of the component (e) may be used in its entirety at the time of dispersing the pigment, or may be used after dispersing a part of the organic solvent. 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. When the amount of the organic solvent used is less than 100 parts by weight at the time of dispersion, the viscosity at the time of dispersion is too high, and dispersion tends to be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a bead mill or the like.

The color filter of the present invention is obtained by applying the above-described photosensitive solution for forming a colored image of the present invention on a substrate and drying the film to form a film, irradiating actinic rays imagewise, and photo-curing the exposed portion. The step of removing unexposed portions by development is repeated for a plurality of different colors to form a pixel. Examples of the method for applying the photosensitive liquid for forming a colored image of the present invention on a substrate include, for example, roll coater coating, spin coater coating, spray coating, whiter coating, dip coater coating, curtain flow coater coating, and wire bar coater coating. , Gravure coater coating, air knife coater coating, and the like. The substrate used at this time is selected depending on the application,
For example, transparent glass substrates such as white plate glass, blue plate glass, silica-coated blue plate glass, and the like, sheets or films or substrates made of synthetic resins such as polyester resin, polycarbonate resin, acrylic resin, and vinyl chloride resin, aluminum plates, copper plates, nickel plates, and stainless steel Examples include a metal substrate such as a plate, a ceramic substrate, and a semiconductor substrate having a photoelectric conversion element. After coating, usually at a temperature of 50 to 150 ° C., 1
The film can be formed by drying for を 30 minutes.

Next, the film on the substrate obtained by the above method is irradiated with actinic rays in an image-like manner to cure the film in the exposed portion. At this time, after forming an oxygen barrier film such as polyvinyl alcohol with a thickness of 0.5 to 30 μm on the surface of the obtained film, exposure can be performed from above. As the light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp,
High-pressure mercury lamp, xenon lamp, metal halide lamp,
Fluorescent lamps, tungsten lamps, visible light lasers and the like can be mentioned. Using these light sources, active rays are irradiated in an image form by pattern exposure through a photomask, direct drawing by scanning, or the like.

Next, a colored image pattern of the cured film corresponding to the image can be obtained by a developing step of removing the unexposed portions. Examples of the developing method include inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, sodium hydrogen carbonate, and sodium tetraborate; monoethanolamine, diethanolamine, and triethanolamine. And a method of spraying an aqueous solution containing an organic alkali such as tetramethylammonium hydroxide, triethylamine, and n-butylamine, and a method of dipping in an aqueous solution.

After development, the colored image pattern is further exposed to light of 0.5 to ⁵ J / 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. Is preferable because the image pattern becomes more robust. The above steps are repeated for a plurality of different colors to form pixels and obtain a color filter.

As a method for producing a color filter used for a liquid crystal display element, for example, the above method is repeated on a glass substrate using the colored image forming photosensitive liquid of the present invention to obtain red, green and blue. After forming colored pixels of
A method for forming a black colored image as a black matrix by using the colored image forming photosensitive liquid (black) of the present invention in the gap between the colored pixels by the above-described method. A method in which a black colored image is formed as a black matrix by the above method using the forming photosensitive liquid (black), and then red, green, and blue colored pixels are formed in the same manner as above. .

[0040]

The present invention will be described below with reference to examples. Synthesis Example 1 (Production of Resin A) 1 equipped with a stirrer, thermometer and cooling pipe
A liter separable flask is charged with 576 g of diethylene glycol dimethyl ether, and then reacted with Oxylac SH-101 (manufactured by Nippon Shokubai; styrene / maleic anhydride (molar ratio 1.5 / 1) copolymer resin). Resin in which maleic acid moiety is half-esterified) 314
g, 2,6-di-tert-butyl-p-cresol 1 g,
1 g of benzyltrimethylammonium chloride and 122.6 g of glycidyl methacrylate were added and dissolved, and while stirring, the temperature was raised to 100 ° C. and kept at the same temperature for 7 hours.
Solid content acid value is 65 (mgKOH / g), solid content (120 ° C, 2
Resin having 40% by weight and a weight average molecular weight of 11,000 (hereinafter, referred to as resin A)
Was obtained.

In the resin A, the glycidyl methacrylate adduct of styrene / monoisopropyl maleate / monoisopropyl maleate had a composition ratio of 1.5 / 0.36 / 0.64 (molar ratio) [60/1.
4.4 / 25.6 (mol%)]. The structure of glycidyl methacrylate adduct of maleic acid monoisopropyl ester is shown below.

Embedded image

Example 1 85 g of a solution of the resin A as the component (a) (solid content 34
g) and 40 g of carbon black as the component (b),
(E) 200 g of propylene glycol dimethyl ether as a component was added, and this was dispersed for 2 hours using a bead mill. 10 g of pentaerythritol tetraacrylate as the component (c), 12 g of benzophenone as the component (d), 4 g of 4,4'-bisdiethylaminobenzophenone, 200 g of propylene glycol monomethyl ether acetate as the component (e) and (f) As a component, 0.2 g of polyethylene glycol (a compound of the general formula (I) wherein R ¹ is a hydrogen atom, p is 4, q and r are 0) was added and mixed to obtain a black colored image forming photosensitive liquid.

This photosensitive solution was applied on a glass substrate (Corning Co., trade name: 7059) by spin coating, followed by drying at 90 ° C. for 3 minutes to form a film having a thickness of 1.0 μm. The obtained film was exposed imagewise at 200 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask.
Subsequently, development was carried out with an aqueous solution containing 3% by weight of triethanolamine to obtain a black image pattern. The optical density of the obtained black image pattern was 2.5.

Further, the adhesion and the photosensitive property of the obtained black image pattern were evaluated by the following methods, and the results are shown in Table 1. Adhesion: 100 squares of 1 mm square were formed with a cutter, and a peeling test was performed using cellophane tape, and the adhesion was evaluated based on the number of squares remaining without peeling. Light sensitivity: The optical density was evaluated as the first step, using a 41-step tablet in which the optical density increased by 0.05 for each step. The larger the value, the better the light sensitivity. Resolution: Evaluated using a negative mask having a pattern having the same line and space width (μm). It is indicated by the minimum line and space width (μm) that can be completely developed, and the smaller the value, the better the resolution.

Example 2 As the component (a), a resin A solution (37.5 g (solid content: 15 g)) and a resin B (methacrylic acid / methyl methacrylate / n-butyl acrylate (16/63/21 (weight ratio)) )) 15 g of a copolymer having a solid content acid value of 104 (mgKOH / g) and a weight average molecular weight of 35,000), 21 g of CI Pigment Red 177 and CI Pigment Yellow with a color index of component (b). 139 to 4
g was added to an organic solvent of 250 g of propylene glycol diethyl ether as the component (e), and this was dispersed for 2 hours using a bead mill. This dispersion is added to the above resin 5
g, 32 g of trimethylolpropane triacrylate as the component (c), and benzophenone 6 as the component (d).
g, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone 50 g of propylene glycol diisopropyl ether and 100 g of propylene glycol monomethyl ether acetate as the component (e) and polyoxyethylene nonylphenyl ether as the component (f) (general formula (I) wherein R ¹ is a nonylphenyl group, R ² is an ethylene group, p is 10, and q and r are 0) (0.2 g), and mixed to obtain a red colored image forming photosensitive liquid.

A 2.0 μm-thick film was formed from the obtained photosensitive solution in the same manner as in Example 1. The obtained film was exposed imagewise at 200 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask. Subsequently, development was carried out with an aqueous solution containing 5% by weight of triethanolamine to obtain a red image pattern. The obtained red image pattern was evaluated for adhesion and photosensitive properties in the same manner as in Example 1. The results are shown in Table 1.

Example 3 As a component (a), 80 g of a solution of resin A (solid content 32
g) and 8 g of Resin B, 15 g of CI Pigment Green 36 and 5 g of CI Pigment Yellow 83, and 200 g of propylene glycol monomethyl ether as the component (e) as the component (b).
Was dispersed using a bead mill for 2 hours. To this dispersion, 32 g of pentaerythritol tetraacrylate as the component (c), 4 g of benzophenone as the component (d), 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone 200 g of propylene glycol monomethyl ether as the component (e) And 0.2 g of polypropylene glycol (a compound of the general formula (I) in which R ¹ is a hydrogen atom, R ² is a propylene group, p is 5, q and r are 0) as a component (f), and mixed. A photosensitive liquid for forming a colored image was obtained.

Further, a film was formed from the obtained photosensitive liquid in the same manner as in Example 2. The obtained film was exposed at 200 mJ / cm ² in the same manner as in Example 2, and then developed to obtain a green image pattern. The obtained green image pattern was evaluated for adhesion and photosensitive properties in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 As a component (a), 60 g of a solution of resin A (solid content 24
g) and 20 g of resin B, and as a component (b), CI Pigment Blue 15: 6 by color index
g and 1 g of CI Pigment Violet 23, (e)
Component propylene glycol monomethyl ether 2
In addition to 60 g, this was dispersed for 2 hours using a bead mill. 30 g of trimethylolpropane triacrylate as component (c), 6 g of benzophenone as component (d), N, N'-tetraethyl-4,4'-
2 g of diaminobenzophenone, 140 g of ethylene glycol monomethyl ether as the component (e) and polyoxyethylene dinonyl phenyl ether as the component (f) (in the general formula (I), R ¹ is a dinonyl phenyl group, R ² is an ethylene group, and p is 0.5 g of a compound (10, q and r = 0) were added and mixed to obtain a blue colored image forming photosensitive liquid.

A film was formed from the obtained photosensitive solution in the same manner as in Example 2. The obtained film was exposed at 200 mJ / cm ² in the same manner as in Example 2, and then developed with an aqueous solution containing 1% by weight of sodium carbonate to obtain a blue image pattern. The adhesion and the photosensitive characteristics of the obtained blue image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 After a black matrix was formed on the glass substrate used in Example 1 by chromium vapor deposition, a red image pattern was formed in the same manner as in Example 2, and after 10 minutes at 180 ° C. Heating was performed. Next, using the substrate, a green image pattern was formed next to the red image pattern in the same manner as in Example 3, and post-heating was performed at 180 ° C. for 10 minutes. Next, using the substrate, a blue image pattern was formed next to the green image pattern in the same manner as in Example 4, and post-heating was performed at 200 ° C. for 10 minutes. As described above, a high-precision and high-quality color filter in which one pixel is composed of three colors of red, green, and blue of 30 μm × 100 μm and has a mosaic of pixels is obtained.

Example 6 A black image pattern (black matrix) was formed on the glass substrate used in Example 1 in the same manner as in Example 1, and post-heating was performed 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 formed of 30 μm × 100 μm red,
A high-precision, high-quality color filter consisting of three colors of green and blue and having pixels arranged in a mosaic pattern was obtained.

Comparative Example 1 A black image pattern was obtained in the same manner as in Example 1 except that the component (f) was not added. The obtained black image pattern was evaluated for adhesion and photosensitive properties in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 A green image pattern was obtained in the same manner as in Example 2, except that the component (f) was not added. The obtained red image pattern was evaluated for adhesion and photosensitive properties in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 A green image pattern was obtained in the same manner as in Example 3, except that the component (f) was not added. The obtained green image pattern was evaluated for adhesion and photosensitive properties in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 4 A green image pattern was obtained in the same manner as in Example 4, except that the component (f) was not added. The adhesion and the photosensitive characteristics of the obtained blue image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0057]

[Table 1]

As can be seen from Table 1, development residues were observed in the colored image forming photosensitive liquids without using the component (f) in the present invention (Comparative Examples 1, 2, 3, and 4). On the other hand, the photosensitive solution for forming a colored image (Examples 1, 2, 3, and 4) produced using the component (f) in the present invention has no development residue,
The resolution was also good. Further, as in Example 5 and Example 6, the color filters produced using the colored image-forming photosensitive liquid of the present invention have excellent depolarization properties of 500 or more and excellent optical properties, and are excellent as image display elements. Was confirmed.

[0059]

According to the first and second aspects of the present invention, the photosensitive liquid for forming a colored image has a wide process latitude, is capable of remarkably reducing undeveloped portions, and can achieve high resolution. The photosensitive liquid for forming a colored image according to the third aspect has the effects of the first aspect of the invention, and further has excellent light sensitivity, heat resistance, and the like. The method for manufacturing a color filter according to claims 4 and 5 has a wide process latitude, can reduce the development residue, and can achieve high resolution. The color filter according to claim 6 is of high precision and high quality.

Claims (6)

[Claims] 1. A resin, (b) a pigment, (c) a monomer having a photopolymerizable unsaturated bond, (d) a photopolymerization initiator,
(E) an organic solvent and (f) the following general formula (I): (Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aryl group having 1 to 14 carbon atoms, and R ² , R ³ and R ⁴ each independently represent an alkylene having 2 to 6 carbon atoms. Represents a group, different from R ² and R ³ , different from R ³ and R ⁴ , p, q
And r are each independently an integer from 0 to 200, and p + q
+ R.gtoreq.1), which contains a compound represented by the formula: 2. The colored image forming photosensitive liquid according to claim 1, wherein (a) the resin has an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000. (A) the resin is a compound represented by the general formula (II): (Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms), and a general formula (II
I) (Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a group having a photoreactive unsaturated bond). 3. The photosensitive liquid for forming a colored image according to 1 or 2. 4. The photosensitive liquid for forming a colored image according to claim 1, 2 or 3, which is coated on a substrate and dried to form a film, which is irradiated with actinic rays in an image form, and the exposed portion is light-cured. A process of removing unexposed portions by development for a plurality of different colors to form pixels. 5. The method according to claim 4, wherein the plurality of different colors are red, green, blue and black. 6. A color filter produced by the method for producing a color filter according to claim 4.