JP5176430B2 - Color filter formed by using coloring composition for spin coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition which is prevented from going around the back surface of a substrate when a color filter is manufactured by applying the colored composition by a spin coating method and to provide the color filter having no coating irregularity which is caused since a flow of the colored composition is ponded by a black matrix. <P>SOLUTION: The colored composition for a spin coating includes: a pigment carrying carrier composed of a transparent resin, its precursor or a mixture of them; a pigment; dimethylsiloxane having a polyether or polyester structure in the main chain thereof; a solvent (S1) having the boiling point of &ge;50&deg;C and &lt;160&deg;C; and another solvent (S2) having the boiling point of &ge;160&deg;C and &lt;250&deg;C. The ratio of the solvent (S2) to the total weight of solvents is 1-20 wt.% and that of the nonvolatile matter content to the total weight of the colored composition is 10-17 wt.%. The colored composition has the surface tension of &ge;27 mN/m and &lt;31 mN/m. The color filter has filter segments formed from the colored composition and the black matrix. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a spin coating coloring composition used for the production of a color filter used for a transmissive / semi-transmissive color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

A color filter has two or more kinds of fine band (striped) filter segments with different hues arranged on the surface of a transparent substrate such as glass (stripe arrangement), or fine filter segments arranged in a fixed arrangement. (Delta arrangement) etc.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a colored composition in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and after removing the solvent by drying, pattern exposure of one filter color is performed, A color filter can be manufactured by removing the exposed portion in the development process to form a first color pattern and, if necessary, applying a process such as heating, and then repeating the same operation for all the filter colors.

  In filter segment formation using a coloring composition containing a pigment, in recent years, a demand for a color filter having a higher color density has increased, and the pigment density in the coloring composition tends to increase. However, when the coloring composition is applied by a spin coating method, the flow characteristics of the coloring composition deteriorate as the pigment concentration increases, and locally in the vicinity of a black matrix (hereinafter referred to as BM), particularly a resin black matrix. The flow of the coloring composition is blocked. As a result, at the point where the flow of the coloring composition is blocked by BM, there is a problem that the film thickness of the coloring composition becomes thin and coating unevenness occurs.

In order to improve the flow characteristics of the colored composition, the problem is solved by lowering the solid content concentration of the colored composition. However, the drying of the colored composition is slowed by lowering the solid content concentration of the colored composition. When the coloring composition is applied by the spin coating method, as disclosed in Patent Document 1, the film thickness is increased particularly at the end face of the substrate, and thus it takes time to dry the end face of the substrate. As a result, the coloring composition wraps around the back surface of the substrate due to the surface tension of the substrate on the end surface of the substrate coated with the coloring composition, and the back surface of the substrate becomes dirty.
JP 2006-80298 A

Then, this invention aims at provision of the coloring composition which can suppress the wraparound of the coloring composition to the back surface of a board | substrate at the time of manufacturing a color filter by applying a coloring composition with a spin coat method. .
Another object of the present invention is to provide a color filter having no coating unevenness resulting from the BM damming.

  The coloring composition for spin coating of the present invention comprises a dye carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a dye, dimethylsiloxane having a polyether structure or a polyester structure in the main chain, and a boiling point of 50 ° C. or higher and 160 ° C. The solvent (S1) having a boiling point of less than 150 ° C. and the solvent (S2) having a boiling point of 160 ° C. or more and less than 250 ° C., and the ratio of the solvent (S2) in the total solvent is 1% by weight or more and 20% by weight or less; The ratio of the non-volatile content in the total amount of is 10 wt% or more and 17 wt% or less, and the surface tension of the colored composition is 27 mN / m or more and less than 31 mN / m.

In the colored composition for spin coating of the present invention, the solvent (S1) is at least one solvent selected from the group consisting of cyclohexanone, 1-methoxy-2-propyl acetate, methylpropylene glycol, and isopentyl acetate. The solvent (S2) is preferably at least one solvent selected from the group consisting of ethyl 3-ethoxypropionate, cyclohexanol acetate, propylene glycol diacetate, and diethylene glycol diethyl ether.
The color filter of the present invention is characterized by comprising a filter segment and a black matrix formed from the colored composition of the present invention.

  By using the colored composition of the present invention, when the colored composition is applied to a substrate by a spin coating method, wrapping of the colored composition to the back surface of the substrate can be suppressed to the minimum, so that BM can be blocked. A color filter having a filter segment with no coating unevenness can be obtained.

First, the coloring composition of the present invention will be described.
The coloring composition of the present invention comprises a dye carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a dye, dimethylsiloxane having a polyether structure or a polyester structure in the main chain, and a boiling point of 50 ° C. or more and less than 160 ° C. Including the solvent (S1) and the solvent (S2) having a boiling point of 160 ° C. or higher and lower than 250 ° C., the ratio of the solvent (S2) in the total solvent is 1% by weight or more and 20% by weight or less. The spin coating coloring composition is characterized in that the proportion of non-volatile content is 10 wt% or more and 17 wt% or less, and the surface tension of the coloring composition is 27 mN / m or more and less than 31 mN / m.
The colored composition of the present invention contains dimethylsiloxane having a polyether structure or a polyester structure in the main chain for the purpose of adjusting the surface tension of the colored composition to 27 mN / m or more and less than 31 mN / m. The surface tension here refers to the surface tension measured by the Wilhelmy method.

  Since the dimethylsiloxane having a polyether structure or polyester structure in the main chain has less cohesive force between molecules than a pendant dimethylsiloxane having a polyether structure or polyester structure bonded to the side chain, the surface of the colored composition during drying Therefore, it is estimated that the number of dimethylsiloxane molecules oriented at the gas-liquid interface is reduced, and the surface tension of the colored composition can be easily adjusted to a range of 27 mN / m or more and less than 31 mN / m. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like, but are not limited thereto. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie, but are not limited thereto. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination.

The addition amount of dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferably 0.003% by weight or more, based on the total weight of the coloring composition (100% by weight), preferably 0.005% by weight or more. It is more preferable that When the addition amount of dimethylsiloxane having a polyether structure or a polyester structure in the main chain is less than 0.003% by weight, when the coloring composition is applied to the substrate by spin coating, the drying rate within the substrate surface is reduced. Coating unevenness (wrinkle unevenness) that appears to be wrinkled due to variation tends to occur. The amount of dimethylsiloxane having a polyether structure or a polyester structure in the main chain is usually 0.5% by weight or less based on the total weight of the coloring composition (100% by weight).
The colored composition of the present invention comprises a solvent (S1) having a boiling point of 50 ° C. or more and less than 160 ° C. and a solvent (S2) having a boiling point of 160 ° C. or more and less than 250 ° C., and the ratio of the solvent (S2) in the total solvent Is 1% by weight or more and 20% by weight or less. The boiling point here means a boiling point under a pressure condition of 760 mmHg.
If the ratio of the solvent (S2) to the total solvent is less than 1% by weight, the coating film is completely dried before the uneven coloring caused by the colored composition being blocked by the resin BM is sufficiently leveled. This is not preferable because a dry coating film with poor coating unevenness can be obtained. On the other hand, if the ratio of the solvent (S2) to the total solvent is more than 20% by weight, the coating film is difficult to dry, and the tackiness is deteriorated.

  Specific examples of the solvent (S1) include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 1-methoxy-2-propyl acetate, methylpropylene glycol, ethyl cellosolve, ethylbenzene, dipropyl ether, Diisopropyl ether, dioxane, trioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetal, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopate Pills, butyl acetate, isobutyl acetate, SEC- butyl, pentyl acetate, isopentyl acetate, acetic SEC- hexyl, methyl propionate, ethyl propionate, and the like butyl propionate. These can be used alone or in combination. Of these, cyclohexanone, 1-methoxy-2-propyl acetate, methylpropylene glycol, and isopentyl acetate are preferable because they exhibit excellent properties in dye dispersibility.

  Specific examples of the solvent (S2) include ethyl 3-ethoxypropionate, propylene glycol diacetate, diethylene glycol dimethyl ether, 3,3,5-trimethylcyclohexanone, cyclohexanol acetate, γ-butyrolactone, tripropylene glycol monomethyl ether (TPM). 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2-methyl-1,3-propanediol, diisobutyl ketone, ethylene glycol monobutyl ether, Ethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl Ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl Acetate, N, N-dimethylacetamide, N-methylpyrrolidone, P-chlorotoluene, O-diethylbenzene, M-diethylbenzene, P-diethylbenzene, O-dichlorobenzene, M-dichlorobenzene, N-butylbenzene, SEC-butylbenzene , T-butylbenzene, cyclohexanol, methylcyclohexanol, dipropylene glycol monobutyl ether , Propylene glycol phenyl ether, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 3-methoxybutanol, 1,3-butylene glycol, 3, , 3,5-trimethyl-2-cyclohexen-1-one, diacetone alcohol, isophorone, dibasic acid ester, benzyl alcohol, propylene glycol monomethyl ether propionate and the like. These can be used alone or in combination. Of these, ethyl 3-ethoxypropionate, propylene glycol diacetate, diethylene glycol diethyl ether, and cyclohexanol acetate are preferable because they exhibit excellent properties in dye dispersibility.

  The surface tension of the colored composition of the present invention is 27 mN / m or more and less than 31 mN / m. When the surface tension is lower than 27 mN / m, it is not preferable because the coating liquid of the coloring composition at the edge of the substrate significantly wraps around the back surface of the substrate due to the surface tension of the substrate. Further, if the surface tension is 31 mN / m or more, the colored composition is remarkably contracted by the surface tension of itself at the end of the substrate immediately after coating, and it is not preferable to coat the end of the substrate sufficiently.

The surface tension of the coloring composition can be controlled by adjusting the type and amount of dimethylsiloxane having a polyether structure or a polyester structure in the main chain and a solvent.
The ratio of the non-volatile content in the total amount of the coloring composition is 10% by weight to 17% by weight, and more preferably 11% by weight to 16% by weight. When the ratio of the non-volatile content in the total amount of the coloring composition is less than 10% by weight, drying of the coloring composition becomes very slow, and the coloring composition remarkably wraps around the back surface of the substrate, which is not preferable. In addition, it takes a long time to dry, and the productivity is also deteriorated. In addition, when the ratio of the non-volatile content in the total amount of the colored composition is larger than 17% by weight, the colored composition is poor in fluidity, so that the colored composition is easily dammed by the BM, and the dried coating film with poor coating unevenness. Is not preferable.

The dye carrier is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.
Examples of the transparent resin include thermoplastic resins, thermosetting resins, and photosensitive resins. Examples of the precursor of the transparent resin include monomers or oligomers that are cured by irradiation with radiation to form a transparent resin, and these can be used alone or in admixture of two or more.

  The dye carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the dye in the coloring composition. Moreover, when using the mixture of transparent resin and its precursor as a pigment | dye carrier, transparent resin is 20-400 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it is 50-250 weight part. Can be used. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the colored composition.

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, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, 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.

  Photosensitive resins include (meth) acrylic compounds and silicate polymers having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the polymer is used. 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.

  Monomers and oligomers that are precursors of transparent resins include 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 (me ) Acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) ) Various acrylates and methacrylates such as acrylate and urethane acrylate, (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 can be mentioned.

As the coloring matter, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be preferably used for the coloring composition of this invention is shown by a color index number.

  Examples of the red coloring composition for forming the red filter segment include C.I. I. PIGMENT RED 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, Red pigments such as H.264 and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

Examples of the yellow coloring composition for forming the yellow filter segment include C.I. I. PI
GMENT YELLOW 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175 It can be used yellow pigments such 176,177,179,180,181,182,185,187,188,193,194,199.

Examples of the orange coloring composition for forming the orange filter segment include C.I. I. Orange pigments such as PIGMENT ORANGE 36, 43, 51, 55, 59, 61 can be used.
Examples of the green coloring composition for forming the green filter segment include C.I. I. PIGMENT
Green pigments such as GREEN 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green coloring composition.
Examples of the blue coloring composition for forming the blue filter segment include C.I. I. PIGMENT
Blue pigments such as BLUE 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 can be used. Blue coloring compositions include C.I. I. PIGMENT VIOLET
Purple pigments such as 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

Examples of the cyan coloring composition for forming the cyan filter segment include C.I. I. Blue pigments such as PIGMENT BLUE 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used.
Examples of magenta colored compositions for forming magenta color filter segments include C.I. I. PIGMENT VIOLET 1, 19, C.I. I. PIGMENT RED 144, 146, 177,
Purple pigments such as 169 and 81, and red pigments can be used. A yellow pigment can be used in combination with the magenta colored composition.

In addition, as inorganic pigments, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (iii)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black And metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.

  In the coloring composition of the present invention, when a pigment is used as a coloring matter, a dispersing aid such as a surfactant, a resin-type pigment dispersing agent, a coloring matter derivative or the like is appropriately used to improve the dispersibility of the pigment in the coloring matter carrier. Can be contained. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition obtained by dispersing the pigment in a dye carrier and an organic solvent using the dispersion aid is used. If so, a color filter excellent in transparency can be obtained. The dispersing aid can be used in an amount of 0.01 to 40 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the dye in the coloring composition.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and fluorine-based and silicone-based surfactants.

  Resin-type pigment dispersant is a resin that has a pigment-affinity part that adsorbs to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, 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 alkyleneimines) 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.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are 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 combination of two or more.

When the colored composition of the present invention is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator is added.
As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-T-butyldichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy Cyclohexyl phenyl ketone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-benzyl-2-dimethylamino-1 Acetophenone photopolymerization initiators such as-(4-morpholinophenyl) -butan-1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone , Benzoylbenzoic acid, benzoylbenzoic acid Benzophenone photopolymerization initiators such as methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthio Thioxanthone photopolymerization initiators such as xanthone and 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-bi Su (trichloromethyl) -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 triazine photopolymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used. A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it is 10-150 weight part.

  The above photopolymerization initiators can be used alone or in combination of two or more. As the sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (T-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone These compounds can also be used in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  In addition, the colored composition 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 hydroquinone compounds such as hydroquinone, methyl hydroquinone, 2,5 di-T-butyl hydroquinone, T-butyl hydroquinone, T-butyl β benzoquinone, T-butyl hydroquinone 2,5 diphenyl-P-benzoquinone, and the like. , Quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine , Phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, triphenylphosphite, trisnonyl Phosphite compounds such as alkenyl phosphites, such as T- butyl pyrocatechol and the like. The storage stabilizer can be used in an amount of 0.001 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

  In addition, the coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to enhance the adhesion between the composition and the transparent substrate. As the silane coupling agent, vinyl tris (β- Methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane and other vinylsilanes, γ-methacryloxypropyltrimethoxysilane and other (meth) acrylsilanes, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltrie Epoxysilanes such as toxisilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldi Aminosilanes such as ethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ- And thiosilanes such as mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the dye in the coloring composition.

  The coloring composition of the present invention comprises one or more dyes, if necessary, in the three-roll mill, two-roll mill, and sand mill in the dye carrier and the organic solvent together with the dispersion aid and the photopolymerization initiator. It can be produced by finely dispersing using various dispersing means such as a kneader and an attritor. Moreover, the coloring composition containing 2 or more types of pigment | dyes can also mix and manufacture what each disperse | distributed separately in the pigment | dye carrier and the organic solvent separately. Dimethylsiloxane having a polyether structure or a polyester structure in the main chain is added when the dye is dispersed in the dye carrier or after the dye is dispersed in the dye carrier.

The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.
The colored composition of the present invention can be prepared as a solvent development type or alkali development type colored resist material. The solvent development type or alkali development type colored resist material is a pigment in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin as a dye carrier, a monomer, a photopolymerization initiator, and an organic solvent. Are dispersed.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a filter segment formed from the colored composition of the present invention and a black matrix on a substrate. For example, a black matrix and red, green, blue, yellow, orange And at least two filter segments selected from cyan and magenta. The said filter segment is formed on a board | substrate by apply | coating the coloring composition of this invention by a spin coat system.

  Color filter substrates include glass plates such as soda-lime glass, low alkali borosilicate glass, and non-alkali aluminoborosilicate glass that have a high transmittance for visible light, and resins such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. A plate is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

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.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples and comparative examples, “parts” means “parts by weight”.

(Preparation of acrylic resin solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., purged with nitrogen in the reaction vessel, and then dropped. N-Butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) from the tube A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30 parts by weight and a weight average molecular weight of 26000.
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 parts by weight. To prepare an acrylic resin solution.

<Preparation of green treated pigment 1 (G1)>
Phthalocyanine green pigment C.I. I. PIGMENT GREEN 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. for 4 hours. Kneaded. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of green-treated pigment 1 (G1) were obtained.

<Preparation of yellow treated pigment 1 (Y1)>
Phthalocyanine green pigment C.I. I. PIGMENT GREEN 36 was changed to azo yellow pigment C.I. I.
490 parts of yellow-treated pigment 1 (Y1) were obtained in the same manner as the preparation of green-treated pigment 1, except that it was changed to PIGMENT YELLOW150 ("E-4GN" manufactured by LANXESS).

<Preparation of blue-treated pigment 1 (B1)>
Blue pigment C.I. I. PIGMENT BLUE15: 6 (Toyo Ink Mfg. Co., Ltd. “Lionol Blue ES”) 200 parts, sodium chloride 1600 parts, and diethylene glycol (Tokyo Kasei Co., Ltd.) 100 parts are charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.). And kneading at 70 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC for 24 hours, and obtained 198 parts of blue process pigment 1 (B1).

<Preparation of red treated pigment 1 (R1)>
Red pigment C.I. I. PIGMENT RED254 (Ciba Specialty Chemicals “
IRGAZIN RED 2030 "), 160 parts of sodium chloride, 1600 parts of sodium chloride, and 190 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C for 10 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC for 24 hours, and obtained 156 parts of red process pigment 1 (R1).

<Preparation of pigment dispersion (GP, YP, BP, RP)>
A mixture of a pigment, a dye derivative, an acrylic resin solution and an organic solvent having the composition shown in Table 2 was uniformly stirred and mixed, and then a zirconia bead having a diameter of 1 mm was used to form an Eiger mill ("Mini Model M-250" manufactured by Eiger Japan). MKII ") for 5 hours. Thereafter, 30.0 parts of cyclohexanone was added to GP, YP, and BP, and 30.0 parts of 1-methoxy-2-propyl acetate was added to RP, followed by filtration with a 5 μm filter to prepare respective pigment dispersions.

Table 1 shows the chemical structure of the dye derivative used to prepare the pigment dispersion.

[Examples 1-7, Comparative Examples 1-10]
The mixture shown in Table 3 was stirred and mixed to be uniform, and then filtered through a 1 μm filter to adjust each color coloring composition (alkali development resist material), and the surface tension was measured.
As a photopolymerization initiator in Table 3, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (“Irgacure 369” manufactured by Ciba Specialty Chemicals) was used. As the ethylenically unsaturated monomer, a dipentaerythritol hexaacrylate / pentaacrylate mixture (“Aronix M402” manufactured by Toagosei Co., Ltd.) was used. Further, as an additive, except for Example 5 and Comparative Examples 1 and 2, dimethylpolysiloxane having a polyether structure in the main chain (“FZ-2122” manufactured by Toray Dow Corning (nonvolatile content: 100% by weight)) A solution obtained by diluting 1 part with 99 parts of cyclohexanone was used. In Example 5, a solution obtained by diluting 4 parts of dimethylpolysiloxane having a polyester structure in the main chain (“BYK-370” (nonvolatile content: 25% by weight) manufactured by Big Chemie) with 96 parts of cyclohexanone was used. In Comparative Example 1, 2 parts of dimethylpolysiloxane having a polyether structure only in the side chain ("BYK-330" (nonvolatile content: 50% by weight) manufactured by Big Chemie) was diluted with 98 parts of 1-methoxy-2-propyl acetate. The solution was used. In Comparative Example 2, no additive was used.
The surface tension was measured at 25 ° C. using CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.
Table 4 shows the boiling points of the solvent used for the preparation of the coloring composition under a pressure condition of 760 mmHg.

About the coloring composition obtained by the Example and the comparative example, the coating nonuniformity derived from BM, the color loss of the edge part of a board | substrate, back surface stain | pollution | contamination, and tack property were evaluated by the following method. The results are shown in Table 5.
(Evaluation of coating unevenness derived from BM)
Examples 1 to 7 and a resin black matrix (BM) for test having a thickness of 3.0 μm, a line width of 30 μm, and an 80 mm square were formed on a glass substrate as shown in FIG. After coating the colored composition obtained in Comparative Examples 1 to 10 and rotating it with a spin coater, a coating film having a thickness of 3.0 μm was formed by vacuum drying at an ultimate vacuum of 1.0 Torr after 30 to 40 seconds. Formed. Spin coating and vacuum drying were performed using (TR28300-CLT (R) manufactured by Tokyo Ohka Kogyo Co., Ltd.) This coated substrate was observed with light box white transmission. The case where the film thickness was thin and radial unevenness occurred in the vicinity of the test BM pattern frame (part A) was marked as x.

(Evaluation of color loss at the edge of the board)
When the colored composition is coated on the coated substrate outside the 2 mm from the edge of the substrate, the colored composition shrinks due to the surface tension at the edge of the substrate, and the colored composition is colored outside the 2 mm from the substrate edge. The case where omission was seen was set as x.
(Backside dirt evaluation)
The case where the coating liquid did not wrap around 5 mm or more from the edge of the substrate toward the center of the substrate on the back surface of the coated substrate was evaluated as ◯.

(Tackiness evaluation)
The coated material was evaluated according to JIS-K5600 on the coated substrate. When the tack was not recognized, it was marked as ◯, and when the tack was confirmed, it was marked as x.
(Samurai evaluation)
When observing the coated substrate in the light box white color transmission in the previous period, x appears to be noticeably wrinkled due to variations in the drying speed in the substrate surface, and it appears to be slightly wrinkled, but there is no practical problem. △, when no wrinkle was visible

In the colored compositions of Examples 1 to 8, all of BM-derived coating unevenness, color loss at the edge of the substrate, backside contamination, and tackiness were good. In the colored composition of Example 6 in which the content of dimethylsiloxane having a polyether structure or a polyester structure in the main chain is less than 0.003 parts by weight, wrinkle unevenness was Δ.
In the colored composition of Comparative Example 1 containing dimethylsiloxane having a polyether structure only in the side chain and having a surface tension of less than 27 mN / m, the coating liquid spilled from the end surface of the back surface of the substrate toward the center by 5 mm or more. Was x. In the colored composition of Comparative Example 2 that did not contain dimethylsiloxane having a polyether structure or a polyester structure in the main chain and had a surface tension of 31 mN / m or more, the colored composition significantly contracted at the edge of the substrate. The coloring composition was not normally applied outside 2 mm from the edge, and the color loss at the edge of the substrate was x. Moreover, wrinkle unevenness was not leveled enough and was x.

In the colored compositions of Comparative Example 3, Comparative Example 5, and Comparative Example 8 in which the ratio of the solvent having a boiling point of 160 ° C. or more and less than 250 ° C. in all the solvents was more than 20% by weight, the drying property was poor and the tack property was x. In the colored compositions of Comparative Example 2, Comparative Example 4, Comparative Example 6, and Comparative Example 9 in which the proportion of the solvent having a boiling point of 160 ° C. or more and less than 250 ° C. in the total solvent is less than 1% by weight, the coating unevenness derived from BM is x. there were.
In the colored compositions of Comparative Example 5, Comparative Example 6, and Comparative Example 7 in which the proportion of the non-volatile content in the total amount of the colored composition is greater than 17% by weight, the colored composition in the spin coat is poor due to poor fluidity of the colored composition. The flow of the product was blocked by BM, and the coating unevenness derived from BM was x. In the colored compositions of Comparative Example 8, Comparative Example 9, and Comparative Example 10 in which the proportion of the non-volatile content in the total amount of the colored composition is less than 10% by weight, drying of the colored composition is slow, so that the center direction from the end surface of the back surface of the substrate The coating liquid spilled over 5 mm, and the back surface contamination was x.

It is the figure which showed the glass substrate in which the resin black matrix (BM) for a test with a film thickness of 3.0 micrometers was formed.

Claims (3)

On the substrate on which the black matrix is formed,
A dye carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a dye, dimethylsiloxane having a polyether structure or a polyester structure in the main chain, a solvent (S1) having a boiling point of 50 ° C. or higher and lower than 160 ° C., and a boiling point of 160 And a solvent (S2) having a temperature not lower than 250 ° C and lower than 250 ° C,
(S1) includes two types of solvents selected from the group consisting of cyclohexanone, 1-methoxy-2-propyl acetate, methylpropylene glycol, and isopentyl acetate,
The ratio of the solvent (S2) in the total solvent is 1% by weight or more and 20% by weight or less, and the ratio of the nonvolatile content in the total amount of the colored composition is 10% by weight or more and 17% by weight or less. A color filter comprising a filter segment made of a coloring composition for spin coating, wherein the surface tension is 27 mN / m or more and less than 31 mN / m . The color filter according to claim 1, wherein the solvent (S1) contains cyclohexanone . The solvent (S2) is at least one kind of solvent selected from the group consisting of ethyl 3-ethoxypropionate, cyclohexanol acetate, propylene glycol diacetate, and diethylene glycol diethyl ether. Color filter.

Images