JP2007140487A - Coloring composition for color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high quality coloring composition for a color filter excellent in stability, excellent also in self solubility after solidification at the end of a coating liquid spout of a die coat system coating device, and having high adhesion between a coated film and a transparent substrate such as glass, and a color filter. <P>SOLUTION: The coloring composition for a color filter contains a dispersing agent (S) represented by the formula (1): (HOOC-)<SB>m</SB>-R<SP>1</SP>-(-COO-[-R<SP>3</SP>-COO-]<SB>n</SB>-R<SP>2</SP>)<SB>t</SB>, a pigment, a monomer-containing pigment carrier (X) and, preferably, a dispersing agent having a basic group, wherein R<SP>1</SP>represents a tetravalent tetracarboxylic acid compound residue; R<SP>2</SP>represents a monoalcohol residue; R<SP>3</SP>represents a lactone residue; m represents 2 or 3; n represents an integer of 1-50; and t represents (4-m). The color filter has filter segments formed using the coloring composition for a color filter. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color composition for a color filter used for forming a filter segment constituting a color filter used in a color liquid crystal display device and a solid-state imaging device, and a color filter obtained using the color composition for a color filter. .

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.
However, in general, it is difficult to obtain a stable dispersion by dispersing fine pigment particles in a pigment carrier such as a varnish, and the dispersion often has a high viscosity due to aggregation of the pigment particles over time, resulting in thixotropic properties. As shown. Such an increase in viscosity and poor fluidity of the composition cause various problems in manufacturing operations and product value. For example, the filter segment of a color filter is generally formed by applying a colored composition in which a pigment is dispersed in a carrier containing a monomer and a resin on a transparent substrate such as glass. If a coloring composition with poor coating properties is used, a coating film having a uniform film thickness cannot be obtained due to poor coating properties, poor leveling, etc.

Further, with the recent increase in size of substrates, a die coating method has been studied as a coating method. Compared with the conventional spin coating method, the die coating method has advantages in that the coating film thickness is more uniform, the coating solution is less wasted, and the coating solution supply circuit is all sealed up to the tip of the coating head.
However, in the die coating method, since the coating solution is exposed to the outside air at the slit opening at the head tip, the coating solution is liable to dry and solidify at the head tip, and the solidified product of the coating solution is clogged with slit nozzles or a transparent substrate. It causes the occurrence of vertical stripe unevenness (vertical application stripes in the application direction) of the coating film applied thereon.
In addition, there is a drawback that the solidified product of the coating solution is detached from the tip of the head, and the coating quality is lowered such as being brought into the coated film as a foreign substance. In order to avoid this, there is a demand for suitability (hereinafter referred to as dry redissolution) that the colored composition for color filter that has been dried and deposited dissolves quickly when it comes into contact with the colored composition for color filter.

In order to improve such a problem, a method using a dispersing agent such as a surfactant or a resin-type dispersing agent is known (for example, see Patent Document 1 and Patent Document 2). However, the use of these dispersants has caused problems such as reduced coating strength, developability, adhesion to transparent substrates such as glass, and durability, and the stability of the color composition for color filters. It was difficult to achieve both compatibility and excellent drying and re-dissolution of the coating solution, and further providing strong adhesion between the coating film and a transparent substrate such as glass.
JP 2003-294935 A JP 2001-164142 A

  Therefore, the present invention is excellent in stability, and further excellent in self-dissolving when solidified at the tip of the coating liquid discharge port of a die coating type coating apparatus, and strong adhesion between a coating film and a transparent substrate such as glass. An object of the present invention is to provide a high-quality coloring composition for a color filter.

The coloring composition for a color filter of the present invention is characterized by containing a dispersant (S) represented by the following formula (1), a pigment, and a pigment carrier (X) containing a monomer.
Formula (1)
^{_{(HOOC-) m -R 1 - (}} - COO - [- R 3 -COO-] n -R 2) t
(Wherein R ¹ is a tetravalent tetracarboxylic acid compound residue, R ² is a monoalcohol residue, R ³ is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4 -M).)
Moreover, the color filter of this invention comprises the filter segment formed using the said coloring composition for color filters, It is characterized by the above-mentioned.

  The coloring composition for a color filter of the present invention is excellent in self-dissolution even when solidified at the tip of the coating liquid discharge port of a die coating type coating apparatus, and is a transparent substrate such as glass while having low viscosity and high fluidity. It is possible to form a coating film having strong adhesion between the two.

First, the coloring composition for a color filter of the present invention will be described.
The coloring composition for a color filter of the present invention comprises a dispersant (S) represented by the following formula (1), a pigment, and a pigment carrier (X) containing a monomer. In particular, the greatest feature is that it contains a dispersant (S) represented by the following formula (1).
Formula (1)
^{_{(HOOC-) m -R 1 - (}} - COO - [- R 3 -COO-] n -R 2) t
(Wherein R ¹ is a tetravalent tetracarboxylic acid compound residue, R ² is a monoalcohol residue, R ³ is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4 -M).)

The dispersant represented by the above formula (1) is characterized by having both a tetravalent tetracarboxylic acid compound residue and a lactone residue, which is excellent in the stability of the coloring composition for color filters, and This results in both re-dissolution of the coating solution and also provides both strong adhesion between the coating film and a transparent substrate such as glass.
The dispersant (S) of the present invention may be synthesized using any production method as long as it has the structure represented by the formula (1), but a lactone is subjected to ring-opening polymerization using a monoalcohol as an initiator. Thus, it is preferable to produce from a first step of producing a polyester having a hydroxyl group at one end, and a second step of reacting the polyester having a hydroxyl group at one end with tetracarboxylic dianhydride.

  The monoalcohol used for the production of the dispersant (S) of the present invention is a compound having one hydroxyl group. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1 -Heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldeca Nord, 2-octyldodecanol, 2-hexyldecanol, aliphatic monoalcohols such as behenyl alcohol, oleyl alcohol, aromatic monoalcohols such as benzyl alcohol, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Propyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol Dimonohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono- 2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene Glycol monomethyl ether, Propylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetra Ethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapro Examples include alkylene glycol monoalkyl ethers such as pyrene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether.

Furthermore, you may use the monoalcohol which has an ethylenically unsaturated double bond as monoalcohol for manufacture of the dispersing agent (S) of this invention.
Examples of the ethylenically unsaturated double bond referred to in the present invention include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferred. These may be single or plural, and may have different types of ethylenically unsaturated double bonds.

  Monoalcohols having an ethylenically unsaturated double bond are classified into 1, 2, and 3 or more depending on the number of ethylenically unsaturated double bonds. Examples of monoalcohols having one ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono ( And (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, and the like.

Examples of the monoalcohol having two ethylenically unsaturated double bonds include 2-hydroxy-3-acryloyloxypropyl methacrylate and glycerin di (meth) acrylate.
Examples of the monoalcohol having 3 ethylenically unsaturated double bonds include pentaerythritol triacrylate, and examples of the monoalcohol having 5 ethylenically unsaturated double bonds include dipentaerythritol pentaacrylate.
Among these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are obtained as a mixture with pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, respectively, so the ratio of monoalcohols by high performance liquid chromatography or hydroxyl value measurement Need to be determined.

  A hydroxyl group at one end obtained by addition polymerization of an alkylene oxide starting from a hydroxyl group of the aliphatic monoalcohol, aromatic monoalcohol, alkylene glycol monoalkyl ether, and monoalcohol having an ethylenically unsaturated double bond exemplified above. Polyalkylene glycols having the formula also fall within the scope of the monoalcohols of the present invention. Further, polyalkylene glycols having a hydroxyl group at one end obtained by addition polymerization of an alkylene oxide to a compound having a phenolic hydroxyl group, such as phenol or cumylphenol, also fall within the scope of the monoalcohol of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. The addition number of alkylene oxide is usually 1 to 300, preferably 2 to 250, and particularly preferably 5 to 100 in one molecule.

The addition of alkylene oxide can be carried out by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. As commercial products, there are UNIOX series manufactured by NOF Corporation and BLEMMER series manufactured by NOF Corporation. Specifically, UNIOX M-400, M-550, M-2000, BLEMMER PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP-1000, PP -500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET series, 30PPT -800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, 10APB-500B, etc.

The monoalcohol used for the production of the dispersant (S) of the present invention is not limited to the above examples, and any compound can be used as long as it is a compound having one hydroxyl group, and it can be used alone. Two or more types may be used in combination.
Among the above monoalcohols, for example, 4-methyl-2-pentanol, isopentanol, isooctanol, 2-ethylhexanol, isononanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol Use of branched aliphatic monoalcohols such as polyalkylene glycols having a hydroxyl group at one end may lower the crystallinity and become liquid at room temperature, so workability and compatibility with other resins This is preferable.

A polyester having a hydroxyl group at one end can be obtained by ring-opening polymerization of a lactone using a monoalcohol as an initiator. Specific examples of the lactone used in the present invention include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. Of these, δ-valerolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone are preferably used in terms of ring-opening polymerizability.
The lactone used in the production of the dispersant (S) of the present invention is not limited to the above exemplified compounds, and may be used alone or in combination of two or more. When two or more types are used in combination, the crystallinity is lowered and may become liquid at room temperature, which is preferable in terms of workability and compatibility with other resins.

Ring-opening polymerization can be carried out in a known manner, for example, in a reactor connected with a dehydrating tube and a condenser, with monoalcohol, lactone, and a polymerization catalyst charged under a nitrogen stream. When a monoalcohol having a low boiling point is used, the reaction can be carried out under pressure using an autoclave. Moreover, when using what has an ethylenically unsaturated double bond in monoalcohol, it is preferable to add a polymerization inhibitor and to react under a dry air flow.
The number of moles of lactone added per mole of monoalcohol is 1 to 50 moles, preferably 3 to 20 moles, and most preferably 4 to 16 moles. When the number of added moles is less than 1 mole, the effect as a dispersant cannot be obtained, and when it is more than 50 moles, the molecular weight of the dispersant becomes too large, leading to a decrease in dispersibility and fluidity.

  Examples of the polymerization catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium. Quaternary ammonium salts such as iodo, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethyl In addition to quaternary phosphonium salts such as suphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, phosphorus compounds such as triphenylphosphine, organic compounds such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate In addition to alkali metal alcoholates such as carboxylates, sodium alcoholates and potassium alcoholates, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, zinc compounds such as zinc chloride, and the like. The amount of the catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. When the catalyst amount is 3000 ppm or more, the resin becomes heavily colored, which adversely affects the stability of the product. On the contrary, if the amount of the catalyst used is 0.1 ppm or less, the rate of ring-opening polymerization of the cyclic ester is extremely slow, which is not preferable.

In the reaction, no solvent or a suitable dehydrated organic solvent can be used. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.
The reaction temperature is 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C. When the reaction temperature is 100 ° C. or lower, the reaction rate is extremely slow, and when the reaction temperature is 210 ° C. or higher, side reactions other than the lactone addition reaction, for example, decomposition of lactone adducts into lactone monomers, formation of cyclic lactone dimers and trimers, etc. tend to occur.
As a polymerization inhibitor used when using a monoalcohol having an ethylenically unsaturated double bond, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, Phenothiazine and the like are preferable. The polymerization inhibitor, alone or in combination, is 0.01 wt% to 6.0 wt%, preferably 0.05 wt% to 1.0 wt%, based on the weight (100 wt%) of the resulting dispersant (S). It can be used in the range of% by weight.

The dispersant (S) of the present invention can be obtained by reacting the hydroxyl group of the polyester having a hydroxyl group at one end obtained in the first step with tetracarboxylic dianhydride (second step). preferable.
The tetracarboxylic dianhydride used in the second step includes an aliphatic or aromatic tetracarboxylic dianhydride, and the aliphatic tetracarboxylic dianhydride includes 1, 2, 3, 4 -Butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 , 3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4 , 5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [ , 2,2] - such oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.

  Examples of the aromatic tetracarboxylic dianhydride include a tetracarboxylic dianhydride having one aromatic ring and a tetracarboxylic dianhydride having two or more aromatic rings. Examples of tetracarboxylic dianhydride having pyromellitic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy- Examples include 1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride. Examples of tetracarboxylic dianhydrides having two or more aromatic rings include ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′ , 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2, , 3,6,7-Naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic acid Dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetra Rubonic acid dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'- Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, Bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride , 9,9-bis (3,4-carboxyphenyl) fluorene dianhydride, such as 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride may be cited.

  The tetracarboxylic dianhydride used in the production of the dispersant (S) of the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydrides. Absent. These may be used alone or in combination. Furthermore, what is preferably used for the production of the dispersant (S) of the present invention is an aromatic tetracarboxylic dianhydride from the viewpoint of lowering the viscosity of the pigment dispersion, and more preferably an aromatic ring having two aromatic rings. It is a tetracarboxylic dianhydride having two or more. In order to improve the contrast ratio of the coating film, tetracarboxylic dianhydride having one aromatic ring is preferable, and pyromellitic dianhydride is more preferable.

The reaction ratio in the second step is as follows: <H> for the number of hydroxyl groups in the polyester having a hydroxyl group at one end, and <N> for the number of anhydrous rings of the tetracarboxylic anhydride. <H> / <N><1.2 is preferable, 0.7 <<H> / <N><1.1, and most preferably <H> / <N> = 1. When the reaction is carried out with <H> / <N><1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water and used.
A catalyst may be used in the second step. Examples of the catalyst include tertiary amine compounds such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 5-diazabicyclo- [4.3.0] -5-nonene and the like.

Both the first step and the second step may be performed without solvent, or an appropriate dehydrated organic solvent may be used. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.
The reaction temperature is 80 ° C to 180 ° C, preferably 90 ° C to 160 ° C. When the reaction temperature is 80 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the half-esterified product again forms a cyclic anhydride, making it difficult to complete the reaction.

  The content of the dispersant (S) in the color filter coloring composition is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 40 parts by weight, still more preferably 5 to 5 parts by weight with respect to 100 parts by weight of the pigment. 30 parts by weight. When the content of the dispersing agent (S) is less than 0.01 parts by weight, the dispersion effect is insufficient, and when it exceeds 100 parts by weight, the dispersibility may be deteriorated.

As a pigment contained in the coloring composition for a color filter of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used.
Below, the specific example of the organic pigment which can be used for the coloring composition for color filters is shown by a color index number.

  Red pigmented compositions for forming red filter segments include, for example, CI 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, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224 Red pigments such as 226, 227, 228, 240, 246, 254, 255, 264, and 272 can be used alone or in combination. A yellow pigment and an orange pigment can be used in combination with the red composition.

  Examples of the yellow coloring composition for forming the yellow filter segment include CI Pigment 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, 16 168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc. Or can be used in combination.

For the orange coloring composition for forming the orange filter segment, for example, CI Pigment orange 36, 43, 51, 55, 59, 61, 71, 73 or the like is used alone or in combination. Can do.
For the green coloring composition for forming the green filter segment, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 or the like can be used alone or in combination. A yellow pigment can be used in combination with the green composition.
Examples of blue coloring compositions for forming blue filter segments include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. Blue pigments can be used alone or in combination. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 can be used in combination with the blue composition.

For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used alone as the cyan coloring composition for forming the cyan filter segment. Or it can mix and use.
The magenta coloring composition for forming the magenta color filter segment includes, for example, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81, alone or in combination. Can be used. A yellow pigment can be used in combination with the magenta composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber And synthetic iron black. 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 for a color filter may contain a dye within a range that does not reduce heat resistance for color matching.

  The pigment carrier (X) containing a monomer contained in the coloring composition for a color filter of the present invention is composed of a monomer alone or a mixture of a monomer and a transparent resin. In the present invention, the monomer means a compound having an ethylenically unsaturated double bond that is cured by irradiation with active energy rays to form a transparent resin, and the monomer has an average molecular weight generally called an oligomer. It includes those having a low polymer of less than about 1000 and having an ethylenically unsaturated double bond.

  As monomers, 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, neopentylglycol Various acrylic acid esters and methacrylic acid esters such as rudiglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate, ( Examples include 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. These can be used alone or in admixture of two or more.

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 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.

  As the photosensitive resin, a (meth) acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is used. Resins in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reaction are used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  Moreover, when forming a filter segment by alkali development using the coloring composition for color filters of the present invention, the pigment carrier (X) preferably contains an alkali-soluble non-photosensitive resin. The alkali-soluble non-photosensitive resin is a resin that dissolves in an alkaline aqueous solution and does not crosslink with radicals. For example, the weight-average molecular weight having an acidic functional group such as a carboxyl group or a sulfone group is 1,000 to 500,000, preferably 5,000 to 100,000. These resins are mentioned. Specific examples of the alkali-soluble non-photosensitive resin include an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfone. Examples thereof include an acid copolymer, an ethylene / (meth) acrylic acid copolymer, and an isobutylene / (anhydrous) maleic acid copolymer. Among them, at least one selected from an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfonic acid copolymer. Resins, particularly acrylic resins having acidic functional groups, are preferably used because of their high heat resistance and transparency.

It is preferable that the coloring composition for color filters of this invention contains the dispersing agent which has a basic group.
Since a dispersant having a basic group excellent in pigment dispersion has a large effect of suppressing reaggregation of the pigment after dispersion, the pigment is dispersed in the pigment carrier by using such a dispersant excellent in pigment dispersion. When a coloring composition dispersed in is used, a color filter excellent in transparency can be obtained. Including a dispersant having a basic group in the colored composition for color filter in the present invention is preferable because the dispersant (S) can form a better adsorption / orientation plane with respect to the pigment.

The blending amount of the dispersant having a basic group is preferably 1 to 40 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the pigment. When the amount of the dispersant having a basic group is less than 1 part by weight, the dispersion effect is insufficient, and when it is more than 40 parts by weight, this may also affect the dispersion.
Examples of the dispersant having a basic group include a resin-type dispersant having a basic group, a surfactant, and a pigment derivative. Among these, the dye derivative (Y) having a basic group that forms better adsorption / orientation with respect to the pigment is preferable.

Examples of the resin-type dispersant having a basic group include basic polymer compounds and aliphatic polyamine / polyester graft polymers. These can be used alone or in admixture of two or more.
Examples of the surfactant having a basic group include anionic interfaces such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, and monoethanolamine of a styrene-acrylic acid copolymer. Activators, alkylbetaines such as alkyldimethylaminoacetic acid betaines, and amphoteric surfactants such as alkylimidazolines. These can be used alone or in admixture of two or more.

The dye derivative (Y) having a basic group is a compound in which a basic substituent is introduced into an organic dye. Examples of the organic dye include azo compounds such as diketopyrrolopyrrole, azo, disazo, and polyazo, Examples include anthraquinone, quinacridone, perinone, perylene, isoindoline, isoindolinone, quinophthalone, selenium, and metal complex dyes. In addition, organic dyes constituting the dye derivatives include light yellow compounds such as acridone, naphthalene, and triazine that are not generally called dyes.
Examples of basic substituents include substituents having an amine moiety, an imine moiety, an ammonium moiety, an amide moiety, an imide moiety, a urethane bond moiety, and the like. Among these, at least one basic group selected from the group represented by the following formula (2), formula (3), formula (4) and formula (5) is preferable.
Formula (2)

式（３）

Formula (3)

式（４）

Formula (4)

式（５）

Formula (5)

X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
v represents an integer of 1 to 10.
R ⁴ , R ⁵ : Each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, or R ⁴ And R ⁵ together represent an optionally substituted heterocyclic residue containing an additional nitrogen, oxygen or sulfur atom.
R ⁶ : Represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group To express.
Y: represents —NR ¹¹ —Z—NR ¹² — or a direct bond.

R ¹¹ and R ¹² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents a group.
Z: represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group.
P: The substituent shown by Formula (6) or the substituent shown by Formula (7) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (6) or a substituent represented by the formula (7).
Formula (6)

式（７）

Formula (7)

  Examples of the amine component used for forming the substituents represented by the formulas (2) to (5) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecyl Min, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopenty Amine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Isonicopetic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. It is done.

ＣｕＰｃは、銅フタロシアニン残基を表す。

化合物２

ＣｕＰｃは、銅フタロシアニン残基を表す。 Specific examples of the dye derivative (Y) having a basic group of the present invention are shown below with compound numbers, but are not limited thereto.
Compound 1

CuPc represents a copper phthalocyanine residue.

Compound 2

CuPc represents a copper phthalocyanine residue.

化合物４

Compound 3

Compound 4

化合物６

Compound 5

Compound 6

化合物８

Compound 7

Compound 8

  In the coloring composition for a color filter of the present invention, a pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as glass so that a dry film thickness is 0.2 to 5 μm to form a filter segment. A solvent can be included to facilitate the process. 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, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These can be used alone or in combination.

When the colored composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition for color filter.
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 nzophenone, 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 (trichloro) Methyl) -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.

  These photopolymerization initiators are used alone or in admixture of two or more. As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenance are used. Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination.

  Moreover, the coloring composition for color filters can contain a storage stabilizer in order to stabilize the viscosity with time of the coloring 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.

  When the filter segment is formed by a photolithography method, the pigment is preferably contained in the color filter coloring composition in a proportion of 1.5 to 15% by weight. Moreover, when forming a filter segment by a printing method, it is preferable to contain in the ratio of 1.5 to 45 weight% in the coloring composition for color filters. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 50% by weight, more preferably 20 to 45% by weight, and the balance substantially consists of a resinous binder provided by the pigment carrier. .

  The color filter coloring composition can be prepared as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent developing type or alkali developing type colored resist material. A solvent development type or alkali development type colored resist material is generally a pigment in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and an organic solvent. Are dispersed.

  The coloring composition for a color filter of the present invention can be produced by finely dispersing a pigment in a pigment carrier using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. . At this time, the dispersing agent (S), the dye derivative (Y), the other resin, and the additive may be dispersed after mixing all of the components. First, the pigment and the dye derivative (Y) alone, or Only the pigment derivative (Y) and the dispersant (S) or only the pigment, the pigment derivative (Y) and the dispersant (S) may be dispersed, and then another component may be added and dispersed again. It can also be produced by mixing several types of pigments separately dispersed on a pigment carrier. The photopolymerization initiator may be added at the stage of preparing the color filter coloring composition, or may be added later to the prepared color filter coloring composition.

  The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. When dispersing the pigment in the pigment carrier, in addition to the dispersant having a basic group that makes the present invention more effective, a dispersant such as a resin-type dispersant and a surfactant may be used in combination as appropriate. it can. These can be used alone or in admixture of two or more.

Next, the color filter of the present invention will be described.
The color filter of this invention comprises the filter segment formed using the coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment, or those having a magenta filter segment, a cyan filter segment, and a yellow filter segment.
As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are 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.

The formation of each color filter segment by photolithography is performed by the following method.
That is, the coloring composition for a color filter prepared as a solvent developing type or alkali developing type colored resist material is dried on a transparent substrate such as glass by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the thickness is 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the color filter can be manufactured by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove an uncured portion and forming a desired pattern.

Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the 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 material, a water-soluble or alkali-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 a printing method, an electrodeposition method, a transfer method, etc. in addition to the above method, but the color filter coloring composition in 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 filter segment is formed in advance on the surface of a peelable transfer base sheet or transfer cylinder, and this filter segment is transferred to a desired transparent substrate.

If a black matrix is formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, an inorganic film such as chromium, a chromium / chromium oxide multilayer film, titanium nitride, or a resin film in which a light shielding agent is dispersed may be used. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.
On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

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”.
Prior to the examples, a method for measuring the contrast ratio of the resist-coated substrate will be described.
A resist material coated substrate is sandwiched between two polarizing plates, and light is irradiated from one polarizing plate side using a backlight unit for liquid crystal display. The light emitted from the backlight unit passes through the first polarizing plate and is polarized, and then passes through the resist material-coated substrate and reaches the second polarizing plate. If the polarization planes of the first polarizing plate and the second polarizing plate are parallel, light passes through the second polarizing plate, but if the polarization plane is perpendicular, the light passes through the second polarizing plate. Are blocked by the polarizing plate. However, when the light polarized by the first polarizing plate passes through the resist material coated substrate, scattering by pigment particles or the like causes a deviation in a part of the polarization plane. When the amount of light transmitted through the second polarizing plate is reduced and the deflecting plate is perpendicular, a part of the light is transmitted through the second polarizing plate.

This transmitted light is measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal is defined as the contrast ratio.
Contrast ratio = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment in the resist material coating film, the luminance when parallel is lowered and the luminance when perpendicular is increased, and the contrast ratio is lowered.
The luminance meter was a color luminance meter BM-5A manufactured by Topcon Corporation, and the polarizing plate was a polarizing film LLC2-92-18 manufactured by Sanritsu. In the measurement, in order to block unnecessary light, measurement was performed by applying a black mask having a 1 cm square hole in the measurement portion.

Next, adjustment of the acrylic resin solutions 1 and 2 and the dispersant (S1 to 7) used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
(Preparation of acrylic resin solution 1)
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained. The weight average molecular weight of the acrylic resin was about 40,000. 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. Thus, an acrylic resin solution 1 was prepared.

(Preparation of acrylic resin solution 2)
370 parts of cyclohexanone was put into a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 35.0 parts of n-butyl methacrylate at the same temperature, 15.0 parts of 2-hydroxyethyl methacrylate, 4.0 parts of 2,2′-azobisisobutyronitrile, 20.0 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M-110” manufactured by Toagosei Co., Ltd.) The mixture was added dropwise over 1 hour to conduct a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained. The weight average molecular weight of the acrylic resin was about 40,000. 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. Thus, an acrylic resin solution 2 was prepared.

(Production Example 1 of Dispersant S1)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. Then, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 73.3 parts of pyromellitic anhydride was added and reacted at 120 ° C. for 2 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a dispersant (S1). The obtained dispersing agent was white solid at normal temperature, and the acid value was 49 mgKOH / g.

[Production Examples 2 to 7 of Dispersant (S)]
Each of the dispersants is obtained by reacting monoalcohol, lactone, and tetracarboxylic dianhydride with a composition as shown in Table 1 using the same apparatus, catalyst, and reaction operation as in Production Example 1 of Dispersant (S). It was.

* Hydroxyl value: 65.8 mgKOH / g (mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate)
(Abbreviations in Table 1)
Methoxy PEG400: One-end methoxylated polyethylene glycol (molecular weight 400)
Blemmer PP500: Polypropylene glycol monomethacrylate (manufactured by NOF Corporation: trade name Blemmer PP-500, hydroxyl value: 95.1 mgKOH / g)
PMA ... Pyromellitic anhydride BPDA ... 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride BPAF ... 9,9-bis (3,4-dicarboxyphenyl) fluorenedioic acid Anhydride NPDA ... 1,4,5,8-naphthalenetetracarboxylic dianhydride TMEG ... ethylene glycol ditrimellitic anhydride ester (manufactured by Shin Nippon Rika Co., Ltd .: trade name Ricacid TMEG-100)
DMBA ... dimethylbenzylamine However, in the production examples 3, 5, and 6 of the dispersant (S), the inside of the reaction vessel was not replaced with nitrogen gas, but was replaced with dry air. In addition, water in Production Example 6 of the dispersant (S) was added after completion of the reaction between the tetracarboxylic dianhydride and the hydroxyl group of the polyester having a hydroxyl group at one end to hydrolyze the remaining acid anhydride. It is.

[Example 1]
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A copper phthalocyanine dispersion was prepared. Dispersant S1 was previously dissolved in cyclohexanone and added.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 10.00 parts (“Heliogen Blue L-6700F” manufactured by BASF)
Dispersant S1 1.00 parts Acrylic resin solution 35.00 parts Cyclohexanone 54.00 parts

Next, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue resist material.
Copper phthalocyanine dispersion 40.00 parts Acrylic resin solution 1 10.50 parts Trimethylolpropane triacrylate 4.50 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
2.00 parts of photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.20 parts Cyclohexanone 42.80 parts

[Examples 2-15, Comparative Examples 1-3]
A pigment, a dispersant, a resin, and a monomer were blended in the proportions (weight ratio) shown in Table 2, and a blue resist material was obtained in the same manner as in Example 1. The solid dispersant was added in advance dissolved in cyclohexanone.

[Examples 16 to 28, Comparative Examples 4 to 6]
Pigments, dispersants, resins, and monomers were blended in the proportions (weight ratios) shown in Table 3, and each color resist material was obtained in the same manner as in Example 1. The solid dispersant was added in advance dissolved in cyclohexanone.

Green pigment: 5.80 parts of copper halide phthalocyanine pigment (CI Pigment Green 36) (“Rionol Green 6YK” manufactured by Toyo Ink Co., Ltd.)
4.20 parts of isoindoline-based pigment (CI Pigment Yellow 139) ("Pariotol Yellow D1819" manufactured by BASF)
Red pigment: 8.33 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254) ("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals)
Anthraquinone pigment (CI Pigment Red 177) 1.34 parts (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals)
Anthraquinone pigment (CI Pigment Yellow 199) 0.33 parts (“Chromoval Yellow GT-AD” manufactured by Ciba Specialty Chemicals)
Yellow pigment: 10.0 parts of isoindoline pigment (CI Pigment Yellow 139) ("Paliotorero D1819" manufactured by BASF)
Monomer: Trimethylolpropane triacrylate (Shin Nakamura Chemical "NK Ester ATMPT")
Initiator: Photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals
Sensitizer: “EAB-F” manufactured by Hodogaya Chemical Co., Ltd.
Solvent: Cyclohexanone compounds 1 to 3, 7, 8: Dye derivatives (Y) exemplified by attaching compound numbers in the specification
Comparative dispersant 1: Phosphoric acid group-containing pigment dispersant “BYK111” manufactured by Big Chemie
Comparative dispersant 2: Phosphoric acid group-containing pigment dispersant “Solspers 41000” manufactured by Abyssia
Dispersant 1: Resin-type dispersant “PB-821” having a basic group manufactured by Ajinomoto Fine Techno Co., Ltd.

(Viscosity stability)
About the coloring composition for color filters obtained by the Example and the comparative example, the viscosity stability was evaluated by the following method.
Using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day after preparing the color filter coloring composition and the time-lapse viscosity accelerated at 40 ° C. for 1 week, The measurement was performed at 25 ° C. under the condition of a rotation speed of 20 rpm. From the values of the initial viscosity and the viscosity with time, the rate of change with time in viscosity was calculated by the following formula.
[Change in viscosity with time] = | ([initial viscosity) − [viscosity with time)) / [initial viscosity] | × 100

(Contrast ratio)
The coloring composition for a color filter obtained in Examples and Comparative Examples was applied to a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater at a rotation speed of 500 rpm, 1000 rpm, and 1500 rpm. Three types of coated substrates having different values were obtained. The resist-coated substrate was dried at 70 ° C. for 20 minutes, exposed to ultraviolet light with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp, heated at 230 ° C. for 1 hour, allowed to cool, and then measured for the contrast ratio. Next, the chromaticity (Y, x, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the three sets of contrast ratio and chromaticity measurement results, the resist material-coated substrate is y = 0.14 for the blue coating, y = 0.60 for the green coating, x = 0.64 for the red coating, For the yellow coating film, the contrast ratio at x = 0.48 was determined using an approximation method.

(Adhesion)
Using the spin coater at a rotation speed at which the film thickness after drying the colored composition for a color filter obtained in Examples and Comparative Examples on a 100 mm × 100 mm, 1.1 mm thick glass substrate is 2.0 μm. The coated substrate is dried at 70 ° C. for 20 minutes, and then exposed to ultraviolet light with a cumulative light quantity of 150 mJ using a super high pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm, and 5% aqueous sodium carbonate solution The unexposed area was washed away and baked in a hot air oven at 230 ° C. for 30 minutes to form a stripe pattern having a width of 100 μm on the substrate.
As a test for adhesion to glass, the chemical resistance of the obtained coating film was evaluated. As a test method, it was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C. for 30 minutes, and the adhesion to the glass before and after immersion was visually observed and evaluated in three stages.
○: No peeling at all Δ: Slight peeling is observed ×: Peeling is recognized

(Presence or absence of resist material solidified from the vertical stripes of the dried coating film and the head tip)
The coloring composition for color filters obtained in Examples and Comparative Examples was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a die coating type coating apparatus, and the resulting coated substrate was 70 ° C. After drying for 20 minutes, a dry coating film was formed, and vertical stripes (vertical coating stripes in the coating direction) of the dried coating film obtained by the following method were evaluated in three stages by visual observation. In addition, the presence or absence of the resist material solidified material detached from the head tip on the dried coating film was evaluated in three stages by visual observation.
Vertical stripe unevenness ○: Vertical stripe unevenness is not recognized at all.
Δ: Slight vertical stripes are observed.
X: Remarkably vertical stripes are observed.
Solidified product ○: No solidified product is observed.
Δ: 1 or more and less than 10 solidified products.
X: 10 or more solidified products.
The results are shown in Table 4.

  The colored compositions for color filters obtained in Examples 1 to 28 are superior in stability over time as compared with those obtained in Comparative Examples 1 to 6, excellent in dry remeltability, glass, etc. It had strong adhesion with the transparent substrate. Among these, the colored compositions for color filters obtained in Examples 2 to 10, 12 to 15, and 17 to 28 using the pigment derivative (Y) having a basic group had good stability over time. Furthermore, when the addition amount of the dispersant (S) is the same, the coloring compositions for color filters of Examples 6, 7, 19, 23, and 27 using the dispersants S2 and S3 as the dispersant (S) Examples 3-5, 13-15, 18, 21, 22, 25, 26, 28 using the dispersants S1, S7 as the dispersant (S), showing the characteristics that the initial viscosity is very low. The coloring composition for color filter showed a feature that the contrast ratio of the coating film was high.

Claims (7)

A coloring composition for a color filter comprising a dispersant (S) represented by the following formula (1), a pigment, and a pigment carrier (X) containing a monomer.
Formula (1)
^{_{(HOOC-) m -R 1 - (}} - COO - [- R 3 -COO-] n -R 2) t
(Wherein R ¹ is a tetravalent tetracarboxylic acid compound residue, R ² is a monoalcohol residue, R ³ is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4 -M).)   Furthermore, the coloring composition for color filters of Claim 1 containing the dispersing agent which has a basic group.   The coloring composition for a color filter according to claim 2, wherein the dispersant having a basic group is a pigment derivative (Y) having a basic group. The pigment derivative (Y) having the basic group has at least one basic substituent selected from the group represented by the following formula (2), formula (3), formula (4) and formula (5). The coloring composition for a color filter according to claim 3.
Formula (2)

Formula (3)

Formula (4)

Formula (5)

X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
v represents an integer of 1 to 10.
R ⁴ , R ⁵ : Each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, or R ⁴ And R ⁵ together represent an optionally substituted heterocyclic residue containing an additional nitrogen, oxygen or sulfur atom.
R ⁶ : Represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group To express.
Y: represents —NR ¹¹ —Z—NR ¹² — or a direct bond.
R ¹¹ and R ¹² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents a group.
Z: represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group.
P: The substituent shown by Formula (6) or the substituent shown by Formula (7) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (6) or a substituent represented by the formula (7).
Formula (6)

Formula (7)

The colored composition for a color filter according to any one of claims 1 to 4, wherein R ¹ of the dispersant (S) is a tetracarboxylic acid compound residue having at least one aromatic ring. . When n of the dispersant (S) is 2 or more, or t is 2 or more, R ³ is selected from pentamethylene, hexamethylene, and alkyl-substituted hexamethylene, and two or more of these are included. The coloring composition for a color filter according to any one of claims 1 to 5.   A color filter comprising a filter segment formed using the color filter coloring composition according to claim 1.