JPH1152563A - Photosensitive liquid for forming colored image, production of color filter using the same and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive liq. preventing uneven coating and capable of improving uniformity of a coating film by containing a phosphoric ester surfactant. SOLUTION: The photosensitive liq. contains a resin, a pigment, a monomer contg. two or more photopolymerizable unsatd. bonds in one molecule, a photopolymn. initiator and a phosphoric ester surfactant. A surfactant having a structure represented by the formula is preferably used as the phosphoric ester surfactant. In the formula, R<5> is 1-18C alkyl or 7-14C alkylaryl, R<6> is OH or R<5> O(CH2 CH2 O)n and (n) is an integer of 0-20 representing the mol number of added ethylene oxide. Then phosphoric ester surfactant is, e.g. lauryl phosphate or polyoxyethylene (n=2 or 4) lauryl ether phosphate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive liquid for forming a colored image used for producing a color filter used for a liquid crystal display device, a sensor, a color separation device and the like, a method for producing a color filter using the same, and The present invention relates to a color filter obtained by the method.

[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 for producing this color filter, a dyeable resin, for example, a material obtained by imparting photosensitivity to natural gelatin or casein is subjected to pattern exposure and development.
A method of forming a colored pixel by mainly dyeing with a dye has been adopted. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials.

In recent years, attention has been paid to a method of forming a colored image by using a photosensitive resin material which is colored by dispersing a pigment, and exposing and developing the photosensitive resin material in order to improve heat resistance and light resistance. Many considerations have been taken. According to this method, it is known that the method for producing a color filter is also simplified, and the obtained color filter is stable and has a long life.

On the other hand, when a photosensitive liquid containing a pixel forming material is applied on a substrate, there is a problem that uneven coating is likely to occur. In particular, when the coating is performed by using the spin coating method, there is a problem that radial unevenness (striation), unevenness in the thickness of the center of rotation, unevenness of the drop of the liquid, and unevenness of the flow of the liquid remain. In order to solve these problems, addition of a silicon-based or fluorine-based leveling agent has been conventionally performed. However, although these conventional leveling agents have the effect of improving the unevenness of radiation and unevenness due to the trace of the flow of liquid, the unevenness of the trace of dripping of the liquid cannot be eliminated.

[0005]

SUMMARY OF THE INVENTION The present invention solves the problem of coating unevenness which is a problem when a solution comprising a photosensitive material in which a pigment is dispersed is applied, and coloration which can remarkably improve the uniformity of the coating film. An object is to provide a photosensitive liquid for image formation.

Another object of the present invention is to provide a method for producing a color filter using the photosensitive solution for forming a colored image and a color filter obtained by the method.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by using a specific surfactant, the appearance of the coating film at the time of coating, particularly the trace of dripping of the liquid, The inventors have found that the unevenness due to the trace of the liquid can be improved and that the effect can be maintained for a long period of time, and based on this finding, the present invention has been completed.

That is, the present invention provides (a) a resin, (b)
A pigment, (c) a monomer containing two or more photopolymerizable unsaturated bonds in a molecule thereof, and (d) a photopolymerization initiator-containing photosensitive solution for forming a colored image, wherein the photosensitive solution is a phosphate ester-based solution. The present invention provides a photosensitive liquid for forming a colored image, comprising: a surfactant.

Further, in the present invention, the above-mentioned photosensitive solution for forming a colored image is applied on a substrate, and then dried to form a film. A process of forming pixels by removing unexposed portions by development using a plurality of photosensitive liquids for forming a colored image of different colors. provide.

Further, the present invention provides a color filter manufactured by the above manufacturing method.

[0011]

The resin which is the component (a) of the photosensitive liquid for forming a colored image of the present invention is not particularly limited, but has an acid value of 20 to 20.
300, weight average molecular weight of 1,500 to 200,000
Resins are preferably used, for example, acrylic acid, methacrylic acid, carboxyl group-containing polymerizable monomers such as itaconic acid, methyl acrylate, acrylates such as ethyl acrylate, methyl methacrylate, methacrylates such as ethyl methacrylate, styrene Copolymers with a polymerizable monomer such as such are exemplified.

From the viewpoint of improving the photosensitivity of the photosensitive solution, a preferred example of the resin (a) is a carboxyl group-containing resin having a photopolymerizable unsaturated bond.

Examples of the carboxyl group-containing resin having a photopolymerizable unsaturated bond include the above-mentioned carboxyl group-containing resin, glycidyl group-containing unsaturated compounds such as glycidyl methacrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxy Ethyl acrylate, 2
-A resin obtained by reacting an unsaturated alcohol such as hydroxyethyl methacrylate, a resin obtained by reacting a free isocyanate group-containing unsaturated compound with a carboxyl group-containing resin having a hydroxyl group, and an addition reaction product of an epoxy resin and an unsaturated carboxylic acid A resin obtained by reacting a polybasic acid anhydride with a polybasic acid anhydride, 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 anhydride, the following general formula ( A repeating unit (I) represented by the following general formula (II) and a repeating unit (III) represented by the following general formula (III); ) And the total of repeating units (II) and (III),
Resins having (I) / {(II) + (III)} of 1 to 5 are exemplified. Among them, from the viewpoint of improving the heat resistance of the pixels and the dispersibility of the pigment, the above-mentioned repeating units (I), (I) II)
And a resin consisting of (III).

[0014]

Embedded image (In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a hydroxyl group or an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ³ each independently represent a 1 to 1 carbon atom.
12 represents an alkyl group, and R ⁴ represents a group having a photopolymerizable unsaturated bond. ) The above repeating units (I) and (I)
As a method for producing a resin comprising I) and (III), for example, a precursor resin comprising repeating units (I) and (II) may be added to an unsaturated alcohol such as allyl alcohol,
A method of producing 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, and the like by an esterification reaction, the precursor resin described above. A compound having one oxirane ring and one ethylenically unsaturated bond, for example, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether,
A method in which a monoalkyl monoglycidyl itaconate or the like is subjected to an addition reaction at a ratio of not more than an equimolar to produce it.

The precursor resin composed of the repeating units (I) and (II) is styrene or a derivative thereof, and a monoalkyl maleate (half ester of maleic acid).
Can be obtained by copolymerizing

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

The monoalkyl maleate includes, for example, mono-C _1-12 alkyl maleate such as monomethyl maleate, monoethyl maleate, mono-n-propyl maleate and mono-maleate.
Isopropyl, mono-n-butyl maleate, mono-n-hexyl maleate, mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-maleate Dodecyl and the like.

The resin comprising the repeating units (I), (II) and (III) thus obtained preferably has an unsaturated equivalent of from 600 to 3,000,
It is more preferably set to 00 to 2,000. If the unsaturated equivalent is less than 600, 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. Further, the molar ratio of the repeating unit (I) to the total of the repeating units (II) and (III), (I) / ｛(II) +
(III)｝ is 1 to 5, more preferably 1 to 3. If the molar ratio is less than 1, the heat resistance of the pixel may decrease, and if it exceeds 5, the solubility of the coating film may decrease.

The acid value of the resin (a) is preferably 20.
~ 300, more preferably 40 ~ 200,
Particularly preferably, it is 60 to 150. If the acid value is less than 20, the alkali developability tends to decrease.
If it exceeds 0, the shape of the image pattern tends to be unclear.

The weight average molecular weight of the resin of component (a) (gel permeation chromatography (GPC)
Measured using a standard polystyrene calibration curve) is preferably from 1,500 to 200,000, more preferably from 5,000 to 100,000, and particularly preferably from 10,000 to 50,000. , 000. If the weight average molecular weight is less than 1,500, the dispersion stability of the pigment tends to decrease. If the weight average molecular weight exceeds 200,000, the viscosity when used as a photosensitive liquid increases, and the coating when coating on a substrate is performed. Properties tend to be reduced, and it is difficult to obtain a uniform coating film.

The above various resins exemplified as the component (a) may be used alone or in combination of two or more. When a resin having a photopolymerizable unsaturated group comprising the above repeating units (I), (II) and (III) is used for the purpose of improving the heat resistance of the pixel and the dispersibility of the pigment, the component (a) The ratio of the resin having a photopolymerizable unsaturated group to the total amount of the resin is 10 to 100.
% By weight, more preferably 30 to 100% by weight.

The amount of the resin (a) used in the present invention is from 10 to 85% by weight based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d). , Preferably 20 to 60% by weight, more preferably 25 to 50% by weight.
% By weight. If the amount is less than 10% by weight, the dispersion stability of the pigment tends to decrease, and if it exceeds 85% by weight, the viscosity of the photosensitive liquid becomes high, and the pigment is applied onto a substrate by spin coating. There is a tendency that the coatability when forming a film is reduced.

As the pigment of the component (b) used in the present invention, any of inorganic pigments and organic pigments can be used, and usually black carbon black (inorganic pigment), graphite (inorganic pigment) and the like are used. Organic pigments are preferred from the viewpoint of rich color tone.

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

When the photosensitive liquid for forming a colored image of the present invention is applied to a color filter, pigments suitable for colored images such as red, green, blue and black are preferably used.

For 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 for toning.

The red pigments include, for example, C.I. I. Pigment Red 9, 123,
155, 168, 177, 180, 217, 220, 2
24 and the like.

As the yellow pigment, for example, C.I. I. Pigment Yellow 20, 2
4, 83, 93, 109, 110, 117, 125, 1
39, 147, 154 and the like.

These red pigments and yellow pigments can be used as a mixture of two or more kinds. In addition,
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.

For a 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.

As the green pigments, for example, C.I. I. Pigment Green 7, 36,
37 and the like.

These green pigments and yellow pigments can be used as a mixture of two or more kinds. In addition,
When using a mixture of a green pigment system and a yellow pigment system, it is preferable to use 50 parts by weight or less of the yellow pigment system based on 100 parts by weight of the total amount of the green pigment system and the yellow pigment system.

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.

The blue pigments include, for example, C.I. I. Pigment Blue 15, 15:
3, 15: 4, 15: 6, 22, 60 and the like.

The purple pigments include, for example, C.I. I. Pigment Violet 19,
23, 29, 37, 50 and the like.

These blue pigments and violet pigments may be used as a mixture of two or more kinds. In addition,
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 amount of the blue pigment and the violet pigment.

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

The amount of the pigment (b) used in the present invention is 5 to 50% by weight based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d). Is preferably set to 10 to 40% by weight, more 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.

As the monomer having two or more photopolymerizable unsaturated bonds in the molecule of the component (c) used in the present invention, for example, EO-modified bisphenol A diacrylate (here, EO means ethylene oxide). The same applies to the following.), ECH-modified bisphenol A diacrylate (here, ECH means epichlorohydrin; the same applies to the following), bisphenol A dimethacrylate,
1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO-modified phosphate diacrylate, ECH-modified phthalate diacrylate,
Polyethylene glycol 400 diacrylate, polypropylene glycol 400 dimethacrylate, tetraethylene glycol diacrylate, ECH-modified 1,6-
Hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate (where PO
Means propylene oxide. The same applies to the following. ), Tris (methacryloxyethyl) isocyanurate, acrylates such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like, and methacrylates corresponding thereto. Can be These monomers are used alone or in combination of two or more.

The monomer of the component (c) in the present invention is
It is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d). And 10 to 30% by weight. When the proportion of the monomer 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.

Examples of the photopolymerization initiator (d) used in the present invention include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 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-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2 -Methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-
Phenanthraquinone, 1,2-benzanthraquinone,
Examples include 1,4-dimethylanthraquinone, 2-phenylanthraquinone, and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer. These photopolymerization initiators are used alone or in combination of two or more.

The amount of the photopolymerization initiator used as the component (d) in the present invention is 0.1% based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d). The content is preferably from 01 to 25% by weight, more preferably from 2 to 20% by weight, and particularly preferably from 5 to 15% by weight. If the amount is less than 0.01% by weight, the photosensitivity tends to decrease, and if it exceeds 25% by weight, the adhesion tends to decrease.

As the phosphate-based surfactant in the present invention, a surfactant having a structure represented by the following general formula (IV) is preferably used.

[0044]

Embedded image (Where R ⁵ is an alkyl group having 1 to 18 carbon atoms or an alkylaryl group having 7 to 14 carbon atoms, and R ⁶ is OH or R ⁵ O
(CH ₂ CH ₂ O) represents _n , and n is an integer of 0 to 20 representing the number of moles of ethylene oxide added. Specifically, lauryl phosphoric acid, polyoxyethylene (n = 2,
4) Lauryl ether phosphoric acid, polyoxyethylene (n
= 2,3,4,6,8,9) nonyl ether phosphate, polyoxyethylene (n = 3, 6, 9) alkyl (C ₁₂ ~
C ₁₅ ) ether phosphoric acid, polyoxyethylene (n = 2,
3) Stearyl ether phosphoric acid, polyoxyethylene (n = 4) oleyl ether phosphoric acid, polyoxyethylene (n = 4, 6) alkyl (C ₁ -C ₈ ) phenyl ether phosphoric acid, polyoxyethylene (n = 4) ) Alkyl (C
₁ -C ₈₎ ether phosphoric acid, polyoxyethylene (n =
8, 11, 15) dialkyl (C ₁ -C ₈ ) phenyl ether phosphoric acid, polyoxyethylene (n = 6) phenyl ether phosphoric acid and the like can be used. These are mixtures of phosphate monoesters and phosphate diesters,
It is commercially available.

The addition amount of the phosphate ester surfactant is preferably 0.01 to 10% based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d).
It is 10% by weight, more preferably 0.05 to 5% by weight, further preferably 0.1 to 1% by weight. 0.01% by weight
If it is less than 10%, the effect of improving the coating unevenness is small, and if it exceeds 10% by weight, the sensitivity tends to decrease, and the developer resistance of the cured film tends to decrease. As the surfactant, a silicon-based surfactant or a fluorine-based surfactant may be used in combination.

The photosensitive liquid for forming a colored image of the present invention comprises, as essential components, (a) a resin, (b) a monomer, (c) a pigment,
(D) In addition to a photopolymerization initiator and a phosphate-based surfactant, thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol for suppressing a dark reaction; an ultraviolet absorber; Various additives such as inhibitors can be used as needed.

Further, the photosensitive solution for forming a colored image of the present invention contains a silane coupling agent having a vinyl group, an epoxy group, an amino group, a mercapto group or the like for improving the adhesion between the coating film and the glass substrate. May be used. The amount of the silane coupling agent used is usually (a), (b), (c)
And (d) is preferably 0.2 to 20 parts by weight based on 100 parts by weight of the total solid content.

The colored image forming photosensitive liquid of the present invention may further contain (e) an organic solvent, if necessary. The photosensitive liquid for forming a colored image of the present invention is a method in which a photosensitive liquid in which each component is uniformly dispersed is directly applied to a substrate and dried to form a coating film, or once applied to a support and dried to form a coating film. After formation, a film is formed on the surface of the substrate by laminating the substrate or the like. Thereafter, exposure and development are performed to obtain a target image pattern.

In order to obtain a photosensitive liquid in which the pigment of the component (b) is uniformly dispersed, the resin of the component (a), the pigment of the component (b) and the surfactant are mixed with the organic solvent of the component (e). Preferably, the mixture is dispersed using a dispersing / kneading apparatus such as an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader.

The organic solvent as the component (e) is not particularly limited, and examples thereof include ketones, cellosolves, alcohols, and aromatics. 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 are used alone or in combination of two or more.

In the dispersion step, anionic pigment dispersants such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, nonionic pigment dispersants such as polyoxyethylene / polyoxypropylene block polymers, etc. Pigment dispersants, anthraquinone-based, perylene-based, phthalocyanine-based, and quinacridone-based organic pigments are introduced with a substituent such as a carboxyl group, a sulfonic acid group, a sulfonate group, a carboxamide group, a sulfonamide group, or a hydroxyl group. Addition of a derivative of an organic dye or the like is preferable because the dispersibility and dispersion stability of the pigment are improved.

These pigment dispersants and organic dye derivatives are
It is preferable to use 50 parts by weight or less based on 100 parts by weight of the pigment.

Further, the monomer of component (c) and the photopolymerization initiator of component (d) may be added at the time of pigment dispersion, and the monomer of component (c) and photopolymerization initiator of component (d) may be added after pigment dispersion. May be added.

The resin of the component (a) may be used in its entirety together with the pigment at the time of dispersion, or a part of the resin may be added after the dispersion. However, it is preferable to use at least 20 parts by weight of the resin 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 dispersion of the pigment, or a part of the organic solvent may be added after the dispersion. However, at least one organic solvent is used 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.
It is preferable to use at least 00 parts by weight. 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 may be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a bead mill or the like.

The organic solvent of the component (e) has a total solid content of 5 to 40% by weight including the components (a), (b), (c) and (d) and the surfactant in the photosensitive solution. It is preferably used so that

Next, a method for producing the color filter of the present invention will be described.

In the method for producing a color filter of the present invention, the above-described photosensitive solution for forming a colored image of the present invention is applied on a substrate, and then dried to form a film, and the film is irradiated with actinic rays in an image-like manner. The step of forming a pixel by photo-curing the exposed part and removing the unexposed part by development is repeated using a plurality of colored image forming photosensitive liquids of different colors, A plurality of pixels of different colors are formed.

Examples of the method for applying the photosensitive liquid for forming a colored image of the present invention on a substrate include roll coater coating, spin coater coating, spray coating, whiter coating, dip coater coating, curtain flow coater coating, and wire bar coating. It is performed by a coater coating, a gravure coater coating, an air knife coater coating, or the like.

The substrate used at this time is selected depending on the application. For example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass, polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin, etc. Examples include a synthetic resin sheet, film or substrate, 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 coating, the coating is preferably dried by blowing heated air (dry air) on the coating or by placing the substrate on a heated hot plate. . The heating temperature of the drying air or the hot plate is usually preferably from 30 to 200 ° C, particularly preferably from 50 to 130 ° C, and the film can be formed by heating for 1 to 30 minutes. The heating temperature may be kept constant during drying, but may be increased stepwise.

The thickness of the dried coating film formed on the substrate surface in this manner is appropriately determined depending on the application, but is usually 0.1
It is used in the range of up to 300 μm. , Preferably 0.2
５5 μm.

Next, a method for forming an image pattern will be described. The film on the substrate obtained by the above method is
An actinic ray is irradiated imagewise to cure the film in the exposed area.
At this time, an oxygen barrier film such as polyvinyl alcohol having a thickness of 0.5 to 30 μm may be formed on the surface of the film on the substrate, and exposure may be performed from above.

As the light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a visible light laser and the like are preferably used. Using these light sources, an active light beam is irradiated in an image form by pattern exposure through a photomask, direct drawing by scanning, or the like. Exposure light amount is usually 10 to 1000 mJ
/ Cm ² , preferably 50 to 500 mJ / cm ² .

Subsequently, a colored image pattern of a cured film corresponding to an image can be obtained by a developing step of removing an unexposed portion.

As the developing method, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-
Examples thereof include a method of spraying an aqueous solution containing an organic base such as butylamine and a salt, and a method of dipping in an aqueous solution.

After development, the colored image pattern is further
0.5 to 5 J / cm using silver lamp etc. ^TwoIrradiate the amount of light
Post-exposure or after 1-60 minutes at 60-200 ° C
Preferably, heating is performed. After this exposure and post-heating
Therefore, the image pattern becomes stronger.

By repeating the above steps using a plurality of colored image forming photosensitive liquids of a plurality of different colors, a color filter having pixels of a plurality of different colors can be manufactured.

As a specific example, a method for producing a color filter used for a liquid crystal display element is illustrated. For example, by repeating the above-described method using the colored image forming material of the present invention on a glass substrate, After forming a colored pixel of blue or the like, 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 chromium vapor deposition or a black colored image first, and Similarly, there is a method of forming a color filter by forming colored pixels such as red, green, and blue.

[0070]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 As a component (a), resin # 24 g shown in Table 1 was added, and as a component (b), 40 g of carbon black was added to 200 g of propylene glycol monomethyl ether, and this was dispersed for 2 hours using a bead mill. This dispersion was added with trimethylolpropane triacrylate 18 as component (c).
g, 10 g of benzophenone as the component (d), N, N '
-Tetraethyl-4,4'-diaminobenzophenone 1
0 g, and γ-methacryloxypropyltrimethoxysilane (trade name: KBM-50, manufactured by Shin-Etsu Silicone Co., Ltd.)
3) 1.5 g of polyoxyethylene stearyl ether phosphoric acid (Phosphor RS-210, trade name of Toho Chemical Industry Co., Ltd.) and 0.5 g of propylene glycol monomethyl ether were added and mixed to form a black colored image of the present invention. A photosensitive solution was obtained.

This photosensitive solution was applied on a glass substrate (Corning Co., Ltd., trade name: 7059) by spin coating, and further dried at 80 ° C. for 5 minutes to form a film having a thickness of 1.0 μm. Table 2 shows the evaluation results of the coating film.

The obtained film was exposed to light in a lattice pattern at 150 mJ / cm ² through an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 6% by weight of triethanolamine to obtain a black matrix pattern. .

Example 2 As a component (a), resin # 40 g shown in Table 1 was added. As a component (b), 25 g of Pigment Red 177 and 1395 g of Pigment Yellow were added to 167 g of propylene glycol monomethyl ether under the color index name. The dispersion was performed for 2 hours using a bead mill. To this dispersion, 27 g of trimethylolpropane triacrylate as the component (c), 6 g of benzophenone as the component (d), 10 g of N, N′-tetraethyl-4,4′-diaminobenzophenone, and further N-β- (N-vinyl 1.5 g of benzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (trade name: SZ-6032, manufactured by Dow Corning Silicone Toray Co., Ltd.), polyoxyethylene alkyl ether phosphoric acid (Phosphor R)
A-600, trade name of Toho Chemical Industry Co., Ltd.) 0.5 g and propylene glycol monomethyl ether 280 g
Was added and mixed to obtain a photosensitive solution for forming a colored image of the present invention.

This photosensitive solution was applied on a glass substrate (trade name: 7059, manufactured by Corn Bing Co., Ltd.) by a spin coating method, and further dried at 80 ° C. for 5 minutes to form a film having a thickness of 2.0 μm. . Table 2 shows the evaluation results of the coating film.

The resulting film was exposed to an image of 150 mJ / cm ² through a negative mask using an ultra-high pressure mercury lamp, and then developed with an aqueous solution containing 6% by weight of triethanolamine to obtain a red image pattern. Was.

Example 3 As a component (a), 40 g of resin B shown in Table 1 were added, and as a component (b), 18 g of Pigment Green 36 and 836 g of Pigment Yellow were added to 200 g of propylene glycol monomethyl ether under the color index name.
This was dispersed for 2 hours using a bead mill. 35 g of pentaerythritol tetraacrylate as the component (c) and benzophenone 12 as the component (d) were added to this dispersion.
g, N, N'-tetraethyl-4,4'-diaminobenzophenone, 3 g, and n-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride (Dow Corning Toray Silicone Co., Ltd. )
(Trade name: SZ-6032) 0.7 g, polyoxyethylene oleyl ether phosphoric acid (Phosphor RB-
410, trade name of Toho Chemical Industry Co., Ltd.) and 0.5 g of propylene glycol monomethyl ether were added and mixed to obtain a photosensitive solution for forming a colored image of the present invention.

This photosensitive solution was applied to a glass substrate and dried in the same manner as in Example 1 to form a film having a thickness of 2.0 μm. Table 2 shows the evaluation results of the coating film.

The obtained film was exposed and developed in the same manner and under the same conditions as in Example 1 to obtain a green image pattern.

Example 4 As the component (a), 36 g of a resin solution B shown in Table 1 was used.
(B) As components, 18 g of Pigment Blue 15: 6 by color index name and Pigment Violet 2
31 1 g of propylene glycol monomethyl ether 2
In addition to this, this was dispersed for 2 hours using a bead mill. 70 g of the above resin solution (solid content 3
8.5 g), 35 g of 1,4-butanediol diacrylate as the component (c), 10 g of benzophenone as the component (d), 2 g of N, N′-tetraethyl-4,4′-diaminobenzophenone, and further γ-methacryloxypropyl 5 g of trimethoxysilane (trade name KBM-503, manufactured by Shin-Etsu Silicone Co., Ltd.), polyoxyethylene lauryl ether phosphoric acid (Phosphor RD-510Y,
0.7 g of Toho Chemical Industry Co., Ltd. and 205 g of propylene glycol monomethyl ether were added and mixed to obtain a photosensitive solution for forming a colored image of the present invention.

This photosensitive solution was applied to a glass substrate and dried in the same manner as in Example 1 to form a film having a thickness of 2.0 μm.
Table 2 shows the evaluation results of the coating film.

The obtained film was exposed and developed under the same method and conditions as in Example 1 to obtain a blue image pattern.

Example 5 A red image pattern was formed on the glass substrate on which the black matrix was formed in Example 1 by the same method and under the same conditions as in Example 2, and post-heating was performed at 150 ° C. for 10 minutes. . Next, using the substrate, a green image pattern was formed next to the red image pattern under the same method and conditions as in Example 3. Thereafter, post-heating was performed at 150 ° C. for 10 minutes. Next, using the substrate, a blue image pattern was formed next to the green image pattern under the same method and conditions as in Example 4. Thereafter, post-heating was performed at 200 ° C. for 10 minutes. As described above, one pixel is 30 μm × 1
A color filter in which pixels were arranged in a mosaic of three colors of red, green, and blue having a size of 00 μm was prepared.

Comparative Example 1 A photosensitive solution was obtained in the same manner as in Example 1, except that 0.5 g of polyoxyethylene stearyl ether phosphoric acid was omitted.

Using this photosensitive liquid, a film having a thickness of 1.0 μm was formed in the same manner and under the same conditions as in Example 1. Table 1 shows the evaluation results of the obtained coating films.

Comparative Example 2 A photosensitive solution was obtained in the same manner as in Example 2, except that 0.5 g of polyoxyethylene alkyl ether phosphoric acid was omitted.

Using this photosensitive liquid, a film having a thickness of 2.0 μm was formed in the same manner and under the same conditions as in Example 2. Table 1 shows the evaluation results of the obtained coating films.

Comparative Example 3 A photosensitive liquid was obtained in the same manner as in Example 3, except that 0.5 g of polyoxyethylene oleyl ether phosphoric acid was omitted.

Using this photosensitive liquid, a film having a thickness of 2.0 μm was formed in the same manner and under the same conditions as in Example 3. Table 1 shows the evaluation results of the obtained coating films.

[0090]

[Table 1]

[0091]

[Table 2] Evaluation of coating film: Visual evaluation with a glass substrate placed on the backlight From Table 1, when the phosphate ester surfactant in the present invention was not used (Comparative Example 1, Comparative Example 2, Comparative Example 3),
The coating film becomes uneven and the uniformity of the coating film decreases. In particular, B
It can be seen that in the case of black for M, the light-shielding properties are not uniform and the display quality is reduced.

On the other hand, in the case of Examples 1 to 4 using the phosphate ester-based surfactant of the present invention, the coating film has no coating unevenness, and the uniformity of the film can be improved. Image patterns can be obtained.

As described above, it was confirmed that the color filter (Example 6) produced by using a colored image forming material having better characteristics than ever before had excellent coating film uniformity and was extremely effective as an image display device. .

[0094]

The photosensitive liquid comprising the colored image forming material of the present invention can suppress unevenness occurring during coating and can significantly improve the uniformity of the coating film.

The color filter produced by the method for producing a color filter of the present invention using these photosensitive liquids can be used as an image display device having excellent optical characteristics.

────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. ⁶ identification symbol FI G03F 7/028 G03F 7/028 7/033 7/033 7/038 501 7/038 501 (72) inventor Akahori Toshihiko Ibaraki Prefecture Hitachi 4-13-1, Higashi-cho, Hitachi City

Claims (7)

[Claims] 1. A colored image formation comprising (a) a resin, (b) a pigment, (c) a monomer containing two or more photopolymerizable unsaturated bonds in a molecule, and (d) a photopolymerization initiator. A photosensitive liquid for forming a colored image, wherein the photosensitive liquid contains a phosphate ester-based surfactant. 2. The colored image forming photosensitive liquid according to claim 1, wherein the resin (a) is a resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000. 3. A resin (a) comprising a repeating unit (I) represented by the following general formula (I), a repeating unit (II) represented by the following general formula (II), and a resin represented by the following general formula (III): The repeating unit (III) represented by the formula (I), wherein the molar ratio of the repeating unit (I) to the total of the repeating units (II) and (III), (I) / {(II) + (III)} is 1 to 5
The photosensitive liquid for forming a colored image according to claim 1, wherein the photosensitive liquid contains a resin that is: Embedded image (In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a hydroxyl group or an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ³ each independently represent a 1 to 1 carbon atom.
12 represents an alkyl group, and R ⁴ represents a group having a photopolymerizable unsaturated bond. ) 4. The colored image forming photosensitive liquid according to claim 1, wherein the phosphate ester-based surfactant is a surfactant having a structure represented by the following general formula (IV). Embedded image (Where R ⁵ is an alkyl group having 1 to 18 carbon atoms or an alkylaryl group having 7 to 14 carbon atoms, and R ⁶ is OH or R ⁵ O
(CH ₂ CH ₂ O) represents _n , and n is an integer of 0 to 20 representing the number of moles of ethylene oxide added. ) 5. A colored image-forming photosensitive liquid according to claim 1, which is applied on a substrate, and then dried to form a film. The film is exposed to actinic rays in an image-like manner and exposed. A color filter characterized by repeatedly performing a process of forming pixels by photo-curing portions and removing unexposed portions by development using a plurality of colored image forming photosensitive liquids of different colors. Manufacturing method. 6. The method for producing a color filter according to claim 5, wherein the method is performed using a photosensitive liquid for forming a red colored image, a photosensitive liquid for forming a green colored image, and a photosensitive liquid for forming a blue colored image. 7. A color filter produced by the method according to claim 5.