JP2007219333A - Color filter and colored composition for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a color filter having excellent color reproducibility and suitable for a color filter for use in a color image pickup tube element, etc. <P>SOLUTION: In a colored composition for color filters, when a coating film is formed, a ratio (T580/560) of transmittance (T580) at a wavelength of 580 nm to transmittance (T560) at a wavelength of 560 nm is 3-15. When a coating film having transmittance of 50% within a wavelength range of 570-580 nm is formed, the coating film has a thickness within a range of 0.5-2.5 μm, spectral transmittance at a wavelength of 430-550 nm is ≤10%, spectral transmittance at a wavelength of 580-590 nm is ≤85% and spectral transmittance at a wavelength of 610-700 nm is ≥90%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color filter mounted on a color imaging device typified by C-MOS, CCD, and the like and a coloring composition for a color filter.

  A color image pickup device such as a CCD performs color separation by disposing color filters each having a primary color filter segment of additive mixture of B (blue), G (green), and R (red) on the light receiving element. Is common. 2. Description of the Related Art In recent years, there has been a demand for a color filter to be attached to an image sensor with a thinner film and a higher concentration of coloring components due to a reduction in area per pixel due to a reduction in size and increase in the number of pixels in a color image sensor.

  The color filter manufacturing method includes a dyeing method using a dye as a color material, a dye dispersion method, a pigment dispersion method using a pigment as a color material, a printing method, and an electrodeposition method. Among these, the dyeing method or the dyeing and dispersing method has a disadvantage that the heat resistance and the light resistance are slightly inferior because the dye is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as the color material of the color filter, and the pigment dispersion method is often used as the manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive in a pigment in which pigment particles, which are pigments, are dispersed in a transparent resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  In order to obtain the color characteristics required in a color filter, it is common to perform toning using two or more kinds of pigments. For the red filter, C.I. I. Pigment Red 177, 208, 224, 254 and the like are used (for example, see Patent Documents 1 to 4). Conventionally, as an ideal spectrum, in the case of a color that does not affect the transmission region of other colors, that is, a red color filter, the transmittance in the green and blue transmission regions is required to be 0%. Furthermore, in order to obtain a good color reproducibility in a color filter used for a color image sensor such as a CCD, a color filter that has a gradual rise from the absorption region to the transmission region in the transmission curve is also required.

However, C.I. I. When Pigment Red 254 is used, the transition from the absorption region to the transmission region in the transmission curve is steep, and there is an undesirable transmission peak in the wavelength region of 520 nm to 540 nm, which affects the transmission region of the green color filter. I will give it.
In addition, C.I. I. When using CI Pigment Red 177 and 224, the rise is slow, but the wavelength at which the transmittance is 50% is slightly shifted to the longer wavelength side, and the transmission peak at 600 nm to 630 nm is lowered. The integrated value of the spectral transmittance every 5 nm in 550 to 700 nm becomes small. Therefore, the red color sensation signal cannot be taken in sufficiently, and in the case of a color filter mounted on the color image sensor, the sensitivity to red is lowered, causing a reduction in red color reproducibility.
From the above points, when the above red pigment is used alone or in combination with another pigment as a main pigment, there is a problem in color reproducibility and high transmittance.

JP 9-325209 A JP-A-10-130547 JP 2000-89025 A JP 2001-51112 A

  The present invention has been made in view of the above circumstances, and has a color composition and a color filter for red color filters that have excellent color reproducibility and high transmittance, and hardly affect the transmission region of other colors. It is a problem to provide.

  In the first invention of the present invention, when a coating film is formed, the ratio (T580 / 560) of the transmittance (T580) at a wavelength of 580 nm to the transmittance (T560) at a wavelength of 560 nm is 3 or more and 15 or less. It is a coloring composition for color filters.

  According to a second aspect of the present invention, when a coating film having a transmittance of 50% is formed within a wavelength range of 570 to 580 nm, the thickness of the coating film is in the range of 0.5 to 2.5 μm, The spectral transmittance at a wavelength of 430 to 550 nm of the coating film is 10% or less, the spectral transmittance at a wavelength of 580 to 590 nm is 85% or less, and the spectral transmittance at a wavelength of 610 to 700 nm is 90% or more. It is a coloring composition for color filters.

  A third invention of the present invention includes a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof, and a pigment. I. Pigment red 48: 1, C.I. I. Pigment Red 177 and the coloring composition for a color filter according to the first or second invention, which is a yellow pigment.

  According to a fourth aspect of the present invention, the ratio (wt%) of each pigment in the pigment is C.I. I. Pigment Red 48: 1 is 1 to 90, C.I. I. The coloring composition for a color filter according to any one of the first to third inventions, wherein Pigment Red 177 is 1 to 30 and Yellow Pigment is 1 to 50.

  A fifth invention of the present invention is a color filter comprising at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one red filter segment is the first It is a color filter formed from the coloring composition for color filters in any one of-4th invention.

  When the color composition for color filter of the present invention forms a coating film, the ratio (T580 / 560) of the transmittance (T580) at a wavelength of 580 nm to the transmittance (T560) at a wavelength of 560 nm is 3 or more and 15 or less. Therefore, a light transmittance curve is obtained in which the rising portion that does not transmit light in the green region and shifts from the absorption region to the transmission region is obtained, and thus good color reproducibility can be obtained.

When the color composition for color filter of the present invention forms a coating film having a transmittance of 50% within a wavelength range of 570 to 580 nm, the thickness of the coating film is in the range of 0.5 to 2.5 μm. Good sensitivity when used as a color filter.
Furthermore, the spectral transmittance of the coating film at a wavelength of 430 to 550 nm is 10% or less, the spectral transmittance of a wavelength of 580 to 590 nm is 85% or less, and the spectral transmittance of a wavelength of 610 to 700 nm is 90% or more. It does not affect the transmission region, has good color separation, and has a large integrated value of spectral transmittance, so that a red color sensation signal can be sufficiently taken in, red sensitivity is high, and color reproducibility is good.

  The coloring composition for a color filter of the present invention includes a pigment carrier composed of a transparent resin, a precursor thereof or a mixture thereof, and the pigment. I. Pigment red 48: 1, C.I. I. Pigment Red 177 and a yellow pigment have good color reproducibility.

  In the coloring composition for a color filter of the present invention, the blending ratio (% by weight) of each pigment in the pigment is C.I. I. Pigment Red 48: 1 is 1 to 90, C.I. I. Since Pigment Red 177 is 1 to 30 and Yellow Pigment is 1 to 50, it has good color reproducibility.

  The color filter of the present invention is a color filter comprising at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one red filter segment is the color filter described above. Therefore, it has high color reproducibility and high transmittance, and hardly affects the transmission region of other colors. Therefore, an excellent color separation color filter can be provided.

Next, the coloring composition for color filters of the present invention will be described in detail with reference to preferred embodiments.
A method for producing a color filter using the coloring composition for a color filter of the present invention is not particularly limited, and a pigment dispersion method, a printing method, an electrodeposition method, and the like can be applied. The case where the pigment dispersion method is used will be specifically described.

  When the color composition for color filter of the present invention forms a coating film, the ratio (T580 / 560) of the transmittance (T580) at a wavelength of 580 nm to the transmittance (T560) at a wavelength of 560 nm is 3 or more and 15 or less. It is necessary to become. Within this range, a light transmittance curve can be obtained in which the light rising in the green region does not transmit and the transition from the absorption region to the transmission region is gentle, so that good color reproducibility can be obtained. (T580 / 560) is particularly preferably 4 or more and 10 or less.

  When (T580 / 560) exceeds 15, the rise of the transmittance curve becomes steep, and good color reproducibility cannot be obtained. If (T580 / 560) is less than 3, the transmittance at 560 nm is high, so that light in the green region is transmitted, and color reproducibility is degraded.

Moreover, when the colored composition for color filters of the present invention forms a coating film having a transmittance of 50% within a wavelength range of 570 to 580 nm, the thickness of the coating film is in the range of 0.5 to 2.5 μm. Preferably there is. More preferably, it is 0.5-1.5 micrometers. The spectral transmittance of the coating film at a wavelength of 430 to 550 nm is preferably 10% or less, the spectral transmittance of a wavelength of 580 to 590 nm is 85% or less, and the spectral transmittance of a wavelength of 610 to 700 nm is preferably 90% or more.
If the above conditions are satisfied, the green and blue transmission regions are not affected in the absorption region of the transmittance curve, and the red transmission is good in the transmission region and the color reproducibility is good.

  Furthermore, the coloring composition for color filters of this invention contains the pigment carrier and pigment which consist of transparent resin, its precursor, or those mixtures. The pigment may be C.I. I. Pigment red 48: 1, C.I. I. It is preferably composed of three types of pigment red 177 and a yellow pigment.

  C. I. When CI Pigment Red 48: 1 is used, the rising portion that shifts from the absorption region to the transmission region in the transmittance curve is near the wavelength of 550 nm. In addition, C.I. I. In Pigment Red 177, a similar rising portion is near the wavelength of 590 nm. Therefore, this C.I. I. Pigment Red 48: 1 is C.I. I. By adjusting the color with Pigment Red 177, a transmittance curve with a gentle rise characteristic can be obtained.

Examples of the yellow pigment used in the present invention include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like.
By using a yellow pigment for toning, C.I. I. It is possible to suppress an increase in transmittance of 500 nm or less, which is a feature of Pigment Red 48: 1.

  The pigment is preferably contained in the color filter coloring composition at a ratio of 1.5 to 7% by weight. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 40% by weight, more preferably 20 to 40% by weight, and the remainder substantially consists of a resinous binder provided by the pigment carrier. .

  The pigment carrier is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin. The precursor of the transparent resin includes a monomer or oligomer that is cured by active energy ray irradiation to form a transparent resin. These can be used alone or in admixture of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group. Examples thereof include a resin obtained by reacting a compound or cinnamic acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  As monomers and oligomers, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopen Tylglycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane Various acrylates and methacrylates such as acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide , N-vinylformamide, acrylonitrile and the like, and these can be used alone or in admixture of two or more.

When the coloring composition for a color filter of the present invention is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p -Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (Trichloromethyl) -s-triazine, 2,4-bis (trick (Romethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.

  In the coloring composition for a color filter of the present invention, the blending ratio (% by weight) of each pigment in the pigment is C.I. I. Pigment Red 48: 1 is 1 to 90, C.I. I. It is preferable that the pigment red 177 is 1 to 30 and the yellow pigment is 1 to 50. More preferably, C.I. I. Pigment Red 48: 1 is 40 to 90, C.I. I. Pigment Red 177 is 5 to 20, and Yellow Pigment is 5 to 40.

  The coloring composition for a color filter of the present invention can be adjusted in the form of a solvent developing type or alkali developing type colored resist. The colored resist is a dispersion of a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or a photosensitive resin and a monomer, and a pigment composition composed of a pigment or two or more pigments is used as necessary. In addition to the photoinitiator, various dispersion means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor can be used to finely disperse in the pigment carrier. The colored composition for a color filter of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

  It is preferable that the coloring composition for color filters of this invention contains a pigment derivative. A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called dyes. Examples of the dye derivative include those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in admixture of two or more. The content of the pigment derivative is preferably 0.001 to 40% by weight, more preferably 1 to 25% by weight, based on the pigment.

  Further, when dispersing the pigment in the pigment carrier, a dispersion aid such as a resin-type pigment dispersant and a surfactant can be appropriately used. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition for a color filter formed by dispersing a pigment in a pigment carrier using a dispersion aid is used. If so, a color filter excellent in transparency can be obtained.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The coloring composition for a color filter of the present invention can contain a solvent. By containing the solvent, the pigment can be sufficiently dispersed in the pigment carrier. Moreover, it becomes easy to apply | coat the coloring composition for color filters on transparent substrates, such as a glass substrate, and it becomes easy to form a filter segment with a dry film thickness of 0.2-2.5 micrometers.

  Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these may be used alone or in combination.

  In addition, the colored composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

  The colored composition for color filter of the present invention is preferably subjected to removal of coarse particles and mixed dust by means such as centrifugation, sintered filter, membrane filter and the like. The size of coarse particles and dust to be removed is preferably 5 μm or more, more preferably 1 μm or more, and particularly preferably 0.5 μm or more.

  The color filter of the present invention comprises at least one red filter segment, at least one blue filter segment, and at least one green filter segment, and the at least one red filter segment comprises the coloring composition for the color filter of the present invention. Formed using.

  The blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. Blue coloring compositions include C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

  Moreover, a green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, and 37 can be used. Green coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 It can be used in combination with the yellow pigments such as 182,185,187,188,193,194,198,199,213,214.

The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate by the printing method or the photolithographic method using the coloring composition for color filters of this invention.
As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When each color filter segment is formed by photolithography, the colored composition prepared as the solvent development type or alkali development type color resist is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. Preferably it is 0.5-2.5 micrometers. If necessary, ultraviolet exposure is performed through a mask having a predetermined pattern provided in contact with or in non-contact with the dried coating film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the color filter coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.
First, production examples of acrylic resin solutions and production examples of pigment dispersions used in Examples and Comparative Examples will be described.

(Preparation of acrylic resin solution)
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Styrene 60.0 parts Methacrylic acid 60.0 parts Methyl methacrylate 65.0 parts Butyl methacrylate 65.0 parts Azobisisobutyronitrile 10.0 parts After the addition, the reaction was further carried out at 100 ° C for 3 hours, and then azobisisobuty A solution of 2.0 parts of nitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain an acrylic resin solution having a weight average molecular weight of about 40000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. To prepare an acrylic resin solution.

(Production of red pigment dispersion 1)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to prepare a red pigment dispersion 1.
C. I. Pigment Red 48: 1 8.0 parts ("Rionol Red 2B FG3300" manufactured by Toyo Ink Manufacturing Co., Ltd.)
Dispersant ("Solspers 20000" manufactured by Zeneca) 1.0 part Acrylic resin solution 40.0 parts Cyclohexanone 51.0 parts

(Production of red pigment dispersion 2)
Among the production of the red pigment dispersion 1, C.I. I. Pigment Red 48: 1 I. A red pigment dispersion 2 was prepared in the same manner as the red pigment dispersion 1, except that the pigment was changed to CI Pigment Red 177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals).

(Production of yellow pigment dispersion 1)
Among the production of the red pigment dispersion 1, C.I. I. Pigment Red 48: 1 I. A yellow pigment dispersion 1 was produced in the same manner as the red pigment dispersion 1 except that it was changed to CI Pigment Yellow 139 (“Pariol Yellow D1819” manufactured by BASF).

(Production of yellow pigment dispersion 2)
Among the production of the red pigment dispersion 1, C.I. I. Pigment Red 48: 1 I. A yellow pigment dispersion 2 was prepared in the same manner as the red pigment dispersion 1, except that the pigment was changed to CI Pigment Yellow 150 ("Yellow Pigment E4GN" manufactured by Bayer).

(Production of yellow pigment dispersion 3)
Among the production of the red pigment dispersion 1, C.I. I. Pigment Red 48: 1 I. A yellow pigment dispersion 3 was produced in the same manner as the red pigment dispersion 1 except that it was changed to CI Pigment Yellow 83 (“Lionol Yellow FG-1842” manufactured by Toyo Ink Manufacturing Co., Ltd.).

[Example 1]
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to prepare an alkali development type red resist material (coloring composition for color filter).
Red pigment dispersion 1 50.0 parts Red pigment dispersion 2 5.0 parts Yellow pigment dispersion 1 20.0 parts Acrylic resin solution 10.0 parts Trimethylolpropane triacrylate 3.0 parts (manufactured by Shin-Nakamura Chemical Co., Ltd. NK ester ATMPT ")
Photoinitiator 1.8 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 10.0 parts

[Example 2]
In the composition of Example 1, an alkali developing type red resist material was prepared in the same manner as in Example 1 except that the yellow pigment dispersion 1 was changed to the yellow pigment dispersion 2.

[Example 3]
In the composition of Example 1, an alkali development type red resist material was prepared in the same manner as in Example 1 except that the yellow pigment dispersion 1 was changed to the yellow pigment dispersion 3.

[Comparative Example 1]
In the composition of Example 1, 50 parts of Red Pigment Dispersion 1 (CI Pigment Red 48: 1) was changed to 55 parts, and 5 parts of Red Pigment Dispersion 2 (CI Pigment Red 177). An alkali-developable red resist was produced in the same manner as in Example 1 except that was changed to 0 part.

[Comparative Example 2]
Except for changing 50 parts of Red Pigment Dispersion 1 (C.I. Pigment Red 48: 1) to 30 parts and changing 5 parts of Red Pigment Dispersion 2 (C.I. Pigment Red 177) to 25 parts. In the same manner as in Example 1, an alkali development type red resist was produced.

[Comparative Example 3]
50 parts of Red Pigment Dispersion 1 (CI Pigment Red 48: 1) is changed to 65 parts, and 5 parts of Red Pigment Dispersion 2 (C.I. Pigment Red 177) is changed to 10 parts. An alkali-developable red resist was produced in the same manner as in Example 1 except that 20 parts of Dispersion 1 (CI Pigment Yellow 139) was changed to 0 part.

  The red resists obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were applied to a glass substrate with a spin coater, dried, exposed, developed, dried again, and a transmittance of 50% at a wavelength of 570 to 580 nm. A coating film was formed to obtain a color filter.

The following evaluation tests were conducted and the results are shown in Table 1.
(Spectral characteristic evaluation)
Using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the transmittance of each color filter was measured. The transmission curve is shown in FIG.
The evaluation rank is as follows: ○: Spectral transmittance at a wavelength of 430 to 550 nm is 10% or less, Spectral transmittance at a wavelength of 580 to 590 nm is 85% or less, Spectral transmittance at a wavelength of 610 to 700 nm is 90% or more, ×: One of the above conditions was not satisfied.

(Thickness evaluation)
The film thickness of the color filter was measured using a surface shape measuring device (“DEKTAK” manufactured by ULVAC).
The ranks of the evaluation were such that the film thickness was ◯: 0.5 to 2.5 μm, ◎: 0.5 to 2.5 μm, and Δ: outside the range of 0.5 to 2.5 μm.

1 and 2, (T580 / 560) of the red color filter obtained using the red resists of Examples 1 to 3 is 4 to 8, and the rising portion of the transmittance curve that shifts from the absorption region to the transmission region Was moderate.
The spectral transmittance at a wavelength of 430 to 550 nm was 10% or less, the spectral transmittance at a wavelength of 580 to 590 nm was 85% or less, and the spectral transmittance at a wavelength of 610 to 700 nm was 90% or more.

  (T580 / 560) of the red color filter obtained using the red resist of Comparative Example 1 exceeds 15, and the rising portion of the transmittance curve that shifts from the absorption region to the transmission region is a steep curve. Reproducibility may be inferior.

(T580 / 560) of the red color filter obtained using the red resists of Comparative Examples 2 and 3 is less than 3, and the rising portion of the transmittance curve transitioning from the absorption region to the transmission region is too gentle. This is because the transmittance at 560 nm is high, and there is a possibility that the color reproducibility is lowered by transmitting light in the green region.
The spectral transmittance at a wavelength of 580 to 590 nm was 85% or less, and the spectral transmittance at a wavelength of 610 to 700 nm was 90% or more. In addition, since the spectral transmittance at a wavelength of 430 to 550 nm or less is a high value exceeding 10%, the green and blue transmission regions are adversely affected and the color reproducibility may be deteriorated.

  The coloring composition for a color filter of the present invention can be applied to an excellent color separation color filter having high color reproducibility and suitable for a color filter used for a color imaging tube element or the like.

It is a graph of the transmission curve in wavelength 400-700nm of the color filter obtained by the Example and the comparative example. It is the graph of the transmission curve which made the wavelength of 550-590 nm the horizontal axis | shaft of FIG.

Claims (5)

  A colored composition for a color filter having a ratio (T580 / 560) of a transmittance (T580) at a wavelength of 580 nm to a transmittance (T560) at a wavelength of 560 nm of 3 or more and 15 or less when a coating film is formed.   When a coating film having a transmittance of 50% is formed within a wavelength range of 570 to 580 nm, the thickness of the coating film is in the range of 0.5 to 2.5 μm, and the coating film has a wavelength of 430 to 550 nm. The coloring composition for a color filter according to claim 1, wherein the transmittance is 10% or less, the spectral transmittance at a wavelength of 580 to 590 nm is 85% or less, and the spectral transmittance at a wavelength of 610 to 700 nm is 90% or more.   A pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof; and the pigment, wherein the pigment is C.I. I. Pigment red 48: 1, C.I. I. The coloring composition for a color filter according to claim 1 or 2, which is CI Pigment Red 177 and a yellow pigment.   The proportion (% by weight) of each pigment in the pigment is C.I. I. Pigment Red 48: 1 is 1 to 90, C.I. I. The coloring composition for a color filter according to any one of claims 1 to 3, wherein Pigment Red 177 is 1 to 30 and Yellow Pigment is 1 to 50.   5. A color filter comprising at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one red filter segment is a color filter according to claim 1. A color filter formed from a coloring composition.

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