JP2002258473A - Color photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color photosensitive composition excellent in heat resistance, light resistance, spectral characteristics and color purity and suitable for the manufacture of a color filter by a photolithographic method. SOLUTION: The color photosensitive composition is prepared by stirring and dissolving a photosensitive resin composition and dyes. Since dyes are used, fine pixels having especially excellent spectral characteristics and color purity can be formed from the obtained color photosensitive composition and bleed-out of dyes by development can be suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive composition suitable for producing a color filter used for a liquid crystal display device or a solid-state image pickup device, a colored cured film pixel thereof, a liquid crystal display device having the same, and a solid-state image pickup device. About.

[0002]

2. Description of the Related Art A liquid crystal display device such as a liquid crystal display (LCD) represented by a notebook personal computer or a liquid crystal television, and a charge coupled device (CCD) used as an input device such as a digital camera or a color copier are represented. Color filters for solid-state imaging devices are necessary.
Methods for manufacturing color filters used in these liquid crystal display devices and solid-state imaging devices include a dyeing method, an electrodeposition method, a printing method, and a pigment dispersion method.

The dyeing method is a method of producing a color filter by dyeing a dyeing base made of a natural resin such as gelatin, glue, casein or the like or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye. Excellent color purity. However, during production, there are problems that it is difficult to uniformly control the dyeing and fixing properties, so that color unevenness is likely to occur, and a dyeing prevention step is required for dyeing, which makes the process complicated.

In the electrodeposition method, a transparent electrode is formed in a predetermined pattern in advance, a resin containing a pigment dissolved or dispersed in a solvent is ionized, and a voltage is applied to produce a color filter on the pattern by applying a voltage. How to In the electrodeposition method, a process including film formation and etching of a transparent electrode for forming a color filter in addition to a transparent electrode for display is required. At this time, if there is a short circuit, a line defect occurs and the yield decreases. In addition, there is a problem that it is difficult to apply to a mosaic arrangement other than the stripe arrangement in principle, and it is difficult to manage the transparent electrodes.

[0005] The printing method is a simple method of producing a color filter by offset printing or the like using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curable resin.
Filtering is difficult due to the high viscosity of the ink that can be used, and defects such as dust, foreign matter and gelled portions of the ink binder are likely to occur, and problems such as positional accuracy, line width accuracy, and flatness due to printing accuracy. There is a point.

[0006] The pigment dispersion method is a method for producing a color filter by a photolithography method using a colored photosensitive composition in which a pigment is uniformly dispersed in a photosensitive resin composition. This method has heat resistance and light resistance due to the use of a pigment, and is suitable for producing a color filter for a large-screen, high-definition color display with sufficient positional accuracy because of patterning by photolithography. However, pigments have problems such as insufficient spectral characteristics and color purity as compared with dyes, less variation of pigments than dyes capable of spectral adjustment of all colors, and a sense of roughness of pixels.

Although there are various methods described above, a pigment dispersion method is mainly used as a method for producing a color filter at present. However, a colored photosensitive composition excellent in all of heat resistance, light resistance, spectral characteristics, color purity, simplification of a manufacturing process, and the like is desired.

[0008]

SUMMARY OF THE INVENTION The present invention has both the characteristics of the dyeing method and the pigment dispersion method, that is, it is excellent in heat resistance, light resistance, spectral characteristics, color purity, simplification of the production process, etc. An object of the present invention is to provide a colored photosensitive composition suitable for producing a color filter by a photolithography method without causing crying.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, the present invention provides (1) a colored photosensitive composition comprising a water-soluble resin, a crosslinkable monomer or oligomer, a photopolymerization initiator, a dye, and an organic solvent. (2) The colored photosensitive composition according to (1), wherein the water-soluble resin is polyvinylpyrrolidone. (3)
The colored photosensitive composition according to (1) or (2), wherein the dye is a dye soluble in an organic solvent. (4) The colored photosensitive composition according to (1) or (2) or (3) is applied on a substrate, and after exposure, the exposed portion is cured, and the non-exposed portion is an activator aqueous solution or an alkaline aqueous solution. Alternatively, a method for producing a color filter, comprising developing and removing with an aqueous solution containing an activator and an alkali and rinsing with water. (5) At least one pixel among the pixels of the color filter manufactured by the method of (4) is (1) or (2),
A color filter which is a cured film of the colored photosensitive composition according to (3). (6) A liquid crystal display device having the color filter according to (5). (7) A solid-state imaging device having the color filter according to (5). Is to provide.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The colored photosensitive composition of the present invention is characterized by containing a water-soluble resin, a photopolymerizable monomer or oligomer, a photopolymerization initiator, a dye and an organic solvent.

The water-soluble resin is characterized in that a resin component is dissolved in water. For example, examples of the water-soluble resin include natural water-soluble resins such as casein, glue, and gelatin, and synthetic water-soluble resins such as polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, polyacrylamide, polyethylene oxide, and polyethyleneimine; methyl cellulose; carboxymethyl cellulose. And other semi-synthetic water-soluble resins. Further, monomers such as vinylpyrrolidone, acryloylmorpholine, (meth) acrylamide, 2-hydroxyethyl (meth) acrylate and the like may be used alone or in combination of two or more kinds, and if necessary, (meth) acrylic acid, styrene, (meth) acrylic acid Esters, (meth) acrylonitrile, vinyl acetate,
A water-soluble resin obtained by polymerizing monomers such as vinyl phenol, vinyl benzoic acid, vinyl butyral, chloroprene, vinyl chloride, and maleic anhydride by radical polymerization, ionic polymerization or the like is used. In particular, polyvinylpyrrolidone has excellent heat resistance and is useful.

The weight average molecular weight (Mw) of the water-soluble resin is 2,000 to 200,000, preferably 3,000 to 2,000.
130,000. When the weight average molecular weight is 2000 or less, or when the weight average molecular weight is 130,000 or more, sensitivity and developability deteriorate. In addition, the total amount of the water-soluble resin is 5 to the total solid content of the colored photosensitive composition.
60 parts by weight, preferably 10 to 40 parts by weight.

Examples of the photopolymerizable monomer or oligomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, Examples include bisphenol-A type epoxy di (meth) acrylate, bisphenol-F type epoxy di (meth) acrylate, and bisphenol-fluorene type epoxy di (meth) acrylate.

These may be used alone or in combination of two or more. The total amount of the photopolymerizable monomer or oligomer is 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on the total solid content of the colored photosensitive composition.

Examples of the photopolymerization initiator include benzyl,
Benzoin methyl ether, benzoin butyl methyl ether, benzoin propyl ether, benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, ester compound of benzoylbenzoic acid, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl Dimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminomethylbenzoate, dimethylaminobenzoic acid isoamide ester, 1- (4-dodecylphenyl) -2-hydroxy-methylpropane-1
-One, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1
-One, 2,2'-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetraphenylbisimidazole,
2,2′-bis (2-chlorophenyl) -4,4 ′,
5,5′-tetra- (4-methoxyphenyl) bisimidazole, 2,4′-bis (trichloromethyl) -6
-(4-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,
3,5-s-triazine, 2,4-bis (tribromomethyl) -6- (4′-methoxyphenyl) -1,3,5
-S-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-triazine, 2benzophenone, benzoylbenzoic acid and the like.

These may be used alone or in combination of two or more. In particular, g-line (436 nm), h-line (405 nm), and i-line (3 nm) of ultraviolet light emitted from an ultra-high pressure mercury lamp generally used as an exposure light source are used.
(65 nm) is preferred. The total amount of the photopolymerization initiator is 0.5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on the total solid content of the colored photosensitive composition.

The dye preferably has a spectrum which can be used for a color filter. Further, in order to form a color filter having excellent spectral characteristics and color purity and having fine pixels, it is preferable to use a dye. In particular, a dye soluble in an organic solvent is selected and used. Acid dyes as these dyes,
Examples include basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, disperse dyes, and oil-soluble dyes. Among them, oil-soluble dyes are preferred. For details of dyes that can be used, refer to Dye Handbook (Maruzen), Dye Chemistry (Syokusha)
And in the Color Chemical Dictionary (CMC)

In general, dyes are difficult to dissolve in organic solvents. For example, in order to increase the solubility of the dye in an organic solvent, for example, an amine salt dye obtained by reacting an acid dye, a basic dye or the like with an amine such as a primary amine or more, for example, an organic amine such as n-propylamine and ethylhexylpropionate. Or a sulfonamide group-containing dye obtained by reacting a sulfonic acid group such as an acid dye or a basic dye with an amine of a primary amine or more, for example, an organic amine such as n-propylamine or ethylhexylpropionate; Is known to increase the solubility. These amine-modified dyes and the like can also be used in the colored photosensitive composition of the present invention.

The dyes may be used alone, but taking advantage of the characteristic of the dyes that can be spectrally prepared in a wide variety of colors, two or more dyes are mixed and dissolved in order to obtain a desired spectrum, and the color tone is adjusted. It may be prepared. The total amount of the dye is 0.5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on the total solid content of the colored photosensitive composition.

The organic solvent includes a water-soluble resin which is a component of the colored photosensitive composition, a photopolymerizable monomer or oligomer,
It is preferable to dissolve the photopolymerization initiator and the dye. Examples of usable organic solvents include benzenes such as benzene, toluene and xylene; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate; and propylene glycol. Propionic acid such as propylene glycol monoalkyl ether acetates such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, and ethyl ethoxypropionate Esters,
Lactate esters such as methyl lactate, ethyl lactate and butyl lactate; diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetates such as methyl acetate, ethyl acetate and butyl acetate; dimethyl ether and diethyl ether;
Ethers such as tetrahydrofuran and dioxane; and ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone.

These may be used alone or in combination of two or more. The amount of the organic solvent added is 50 to 2,000 parts by weight based on the total solid content of the colored photosensitive composition,
Preferably it is 100 to 1000 parts by weight.

The colored photosensitive composition of the present invention is produced by stirring and dissolving the water-soluble resin, photopolymerizable monomer or oligomer, photopolymerization initiator, dye, and organic solvent with a dissolver, a homomixer, or the like. You. Further, the colored photosensitive composition is prepared by diluting with the above-mentioned organic solvent so as to have a solid content of 5 to 50% by weight, preferably 10 to 25% by weight, in order to adjust the film thickness at the time of application by a spin coater.

The colored photosensitive composition may further contain, if necessary, various additives such as a filler, a surfactant, a thermal polymerization inhibitor, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent. Can be blended. Furthermore, it is manufactured by precision filtration with a filter or the like to remove foreign substances and the like for shipment as a product.

Further, in the color filter of the present invention, at least one color pixel comprises a cured film of the above colored photosensitive composition. For example, for a color filter composed of three colors, 1
The color or two-color pixels may be the above-described colored photosensitive composition, and the other remaining color pixels may be a pigment-dispersed colored photosensitive composition containing a pigment. The colored photosensitive composition described above may be used. Examples of the pigment used in the pigment-dispersed colored photosensitive composition include red: C.I.
I. Pigment Red 177, 254, green: C.I. I. Pigment Green 7, 36,
Blue: C.I. I. Pigment Blue 15:
6, 60, yellow: C.I. I. Pigment Yel
low 83, 139, 150, magenta: C.I. I. P
Pigment Red 81, 122, 209, cyan: C.I. I. Pigment Blue 15: 3 and the like, and a pigment-dispersed colored photosensitive composition which is prepared and contained in desired spectral characteristics.

To produce a color filter, for example, the colored photosensitive composition of the present invention is applied to a glass substrate, a silicon substrate or the like by a spin coating method, a roll coating method, a bar coating method or the like so as to have a film thickness of 0. It is applied so as to have a thickness of 1 to 5 μm, and prebaked to form a film. Next, radiation (for example, electron beam, ultraviolet light, preferably ultraviolet light) is irradiated through a predetermined mask pattern by a photolithography method, developed with an aqueous solution of an activator or an aqueous alkali solution or an aqueous solution of (activator + alkali), and an unirradiated portion is removed. After rinsing with water, a treatment such as post baking is performed to obtain a colored cured film pixel.

The liquid crystal display device having a color filter composed of pixels of the colored cured film of the colored photosensitive composition of the present invention comprises:
A backlight, a polarizing film, a display electrode, a liquid crystal, an alignment film, a common electrode, a color filter of the present invention, a polarizing film, and the like are manufactured in a laminated structure in this order, and the solid-state imaging device includes a transfer electrode and a photodiode. On a silicon wafer, provided a color filter layer of the present invention,
Then, it is manufactured by laminating micro lenses. The primary colors of the color filters are red, green, and blue, and the complementary colors are yellow, magenta, cyan, and green.

[0027]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Production of Colored Photosensitive Composition (Yellow) As a water-soluble resin, polyvinylpyrrolidone K30 (BAS)
F) 0.347 g, DPHA (manufactured by Nippon Kayaku) as a photopolymerizable monomer or oligomer 0.347 g, triazine A (manufactured by Sanwa Chemical) 0.17 as a photopolymerization initiator
35 g, 0.36 g of PC Yellow 42P (manufactured by Nippon Kayaku) as a pigment, and 6 g of ethyl lactate (manufactured by Musashino Chemical) as an organic solvent are stirred and dissolved with a dissolver, and further subjected to microfiltration with a 0.2 μm membrane filter, followed by color photosensitivity. A composition (yellow) was obtained. The obtained colored photosensitive composition was applied on a glass substrate, formed into a film, and observed under a microscope. As a result, no foreign matter was observed, and the film was glossy and uniform.

(2) Colored image formation (yellow) The colored photosensitive composition (yellow) obtained in (1) was formed into a thermosetting base film having a thickness of 0.3 μm on a silicon wafer. Was applied by a spin coater to a film thickness of 1 μm, and prebaked on a hot plate at 80 ° C. for 100 seconds. Next, using a 500 W ultra-high pressure mercury lamp, energy of 1000 mJ / cm 2 was irradiated through a mask on which a square pixel pattern of 5 μm was drawn. Thereafter, development was performed using an activator aqueous solution at a liquid temperature of 25 ° C. After washing with water and post-baking on a hot plate at 180 ° C., the transfer pattern was observed with a microscope. As a result, a 5 μm square pixel pattern having excellent resolution and adhesion and having no residue was obtained. Further, the dye did not cry due to the development, the color purity was excellent, and the spectral characteristics did not change.

Example 2 (3) Production of Colored Photosensitive Composition (Magenta) As a water-soluble resin, polyvinylpyrrolidone K30 (BAS)
F) 0.347 g, DPHA (manufactured by Nippon Kayaku) 0.347 g as a photopolymerizable monomer or oligomer, and triazine A (manufactured by Sanwa Chemical) 0.17 as a photopolymerization initiator
35 g, 0.3 g of a sulfonamide obtained by modifying PC Magenta 41P (manufactured by Nippon Kayaku) as a dye with EHP amine, and ethyl lactate (manufactured by Musashino Chemical) as an organic solvent
6 g was stirred and dissolved by a dissolver, followed by microfiltration with a 0.2 μm membrane filter to obtain a colored photosensitive composition (magenta). The obtained colored photosensitive composition was applied on a glass substrate, formed into a film, and observed under a microscope. As a result, no foreign matter was observed, and the film was glossy and uniform.

(4) Formation of Colored Image (Magenta) The colored photosensitive composition (magenta) obtained in (3) was formed on a silicon wafer by forming a thermosetting base film with a thickness of 0.3 μm on a silicon wafer. Was applied by a spin coater to a film thickness of 1 μm, and prebaked on a hot plate at 80 ° C. for 100 seconds. Next, using a 500 W ultra-high pressure mercury lamp, energy of 1000 mJ / cm 2 was irradiated through a mask on which a square pixel pattern of 5 μm was drawn. Thereafter, development was performed using an activator aqueous solution at a liquid temperature of 25 ° C. After washing with water and post-baking on a hot plate at 180 ° C., the transfer pattern was observed with a microscope. As a result, a 5 μm square pixel pattern having excellent resolution and adhesion and having no residue was obtained. Further, the dye did not cry due to the development, the color purity was excellent, and the spectral characteristics did not change.

Example 3 (5) Production of Colored Photosensitive Composition (Cyan) As a water-soluble resin, polyvinylpyrrolidone K30 (BAS)
F) 0.347 g, DPHA (manufactured by Nippon Kayaku) 0.347 g as a photopolymerizable monomer or oligomer, and triazine A (manufactured by Sanwa Chemical) 0.17 as a photopolymerization initiator
35 g, Neozapon Blue 80 as a dye
7 (manufactured by BASF) and 6 g of ethyl lactate (manufactured by Musashino Chemical) as an organic solvent were stirred and dissolved with a dissolver, followed by microfiltration with a 0.2 μm membrane filter to obtain a colored photosensitive composition (cyan). . The obtained colored photosensitive composition was applied on a glass substrate, formed into a film, and observed under a microscope. As a result, no foreign matter was observed, and the film was glossy and uniform.

(6) Colored image formation (cyan) The colored photosensitive composition (cyan) obtained in (5) was formed on a silicon wafer by forming a thermosetting base film with a thickness of 0.3 μm on a substrate. Was applied by a spin coater to a film thickness of 1 μm, and prebaked on a hot plate at 80 ° C. for 100 seconds. Next, using a 500 W ultra-high pressure mercury lamp, energy of 1000 mJ / cm 2 was irradiated through a mask on which a square pixel pattern of 5 μm was drawn. Thereafter, development was performed using an activator aqueous solution at a liquid temperature of 25 ° C. After washing with water and post-baking on a hot plate at 180 ° C., the transfer pattern was observed with a microscope. As a result, a 5 μm square pixel pattern having excellent resolution and adhesion and having no residue was obtained. Further, the dye did not cry due to the development, the color purity was excellent, and the spectral characteristics did not change.

Example 4 Preparation of Complementary Color Filter A complementary color filter was prepared by repeating steps (2) of Example 1, (4) of Example 2, and (6) of Example 3. I can do it. In this step, green is obtained by overlapping yellow and cyan.
When the transfer pattern of the obtained complementary color filter was observed with a microscope, it was confirmed that the mixed color, no color loss, resolution,
A 5 μm color filter having excellent adhesion and no residue was obtained. Further, the dye did not cry due to the development, the color purity was excellent, and the spectral characteristics did not change.

The colored photosensitive composition of the present invention has heat resistance,
It is a suitable colored photosensitive composition that is excellent in light resistance, spectral characteristics, color purity, simplification of the production process, and the like, and that can produce a color filter by a photolithography method. Since a dye is used, it is possible to form a fine pixel having particularly excellent spectral characteristics and color purity, so that a color filter used for a liquid crystal display device or a solid-state imaging device can be easily manufactured.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/1335 505 G02F 1/1335 505 G03F 7/033 G03F 7/033 F term (reference) 2H025 AA04 AA10 AA11 AB13 AC01 AD01 BC13 BC42 CA00 CB08 CB41 CB53 CC03 CC13 FA17 2H048 BA02 BA45 BA48 BB02 BB14 BB42 2H091 FA02Y FA08X FA08Z FA41Z LA04 LA12 LA16 4J011 PA74 PB25 PC08 QA03 QA13 QA22 QA34 SA01 SA01 SA01 SA01 SA01 AA61 AC30 AC35 BA27 BA28 BA29 BA30 DB06 DB24 DB36 FA05 GA06 GA08

Claims (7)

[Claims] 1. A colored photosensitive composition comprising a water-soluble resin, a photopolymerizable monomer or oligomer, a photopolymerization initiator, a dye, and an organic solvent. 2. The colored photosensitive composition according to claim 1, wherein said water-soluble resin is polyvinylpyrrolidone. 3. The colored photosensitive composition according to claim 1, wherein the dye is a dye soluble in an organic solvent. 4. The colored photosensitive composition according to claim 1 or 2, applied on a substrate, and after exposure, the exposed portion is cured, and the unexposed portion is exposed to an aqueous solution of an activator, an aqueous alkaline solution or an aqueous solution of an active agent. A method for producing a color filter, comprising developing and removing with an aqueous solution containing an agent and an alkali and rinsing with water. 5. A color filter wherein at least one pixel of the pixels of the color filter produced by the method of claim 4 is a cured film of the colored photosensitive composition according to claim 1. 6. A liquid crystal display device having the color filter according to claim 5. 7. A solid-state imaging device having the color filter according to claim 5.