JP7107198B2 - Pigment dispersant and pigment composition, coloring composition and color filter using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a pigment dispersant, a pigment composition, a coloring composition and a color filter using the same.

In a liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light that has passed through the first polarizing plate, and controls the amount of light that passes through the second polarizing plate. A type that uses a twisted nematic (TN) type liquid crystal is the mainstream. Other representative methods of liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and an electric field is applied in a direction parallel to the substrate, and negative dielectric anisotropy. vertical alignment (VA) method for vertically aligning nematic liquid crystals, and optically convergent bend (OCB) method for optical compensation by making the optical axes of uniaxial retardation films orthogonal to each other. etc., and each has been put to practical use.

A liquid crystal display device has become capable of color display by providing a color filter between two polarizing plates, and has been used in televisions, personal computer monitors, and the like in recent years.

A color filter consists of two or more fine stripe-shaped filter segments of different hues arranged in parallel or crossing on the surface of a transparent substrate such as glass, or fine filter segments arranged in a constant vertical and horizontal arrangement. It consists of those arranged in The filter segments are as fine as several microns to several hundred microns, and are arranged orderly in a predetermined arrangement for each hue.

Quality items required for color filters include brightness and contrast ratio. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed. state), the transmitted light is attenuated, resulting in a blurry screen. Therefore, in order to realize a high-quality liquid crystal display device, it is essential to increase the contrast.

In addition, if a color filter with low luminance is used, the light transmittance is low, resulting in a dark screen. To make the screen bright, it is necessary to increase the number of backlights, which are light sources. Therefore, from the viewpoint of suppressing an increase in power consumption, there is a trend toward increasing the luminance of color filters.

Liquid crystal display devices are mounted not only on televisions and the like, but also on portable terminals and the like, so there is also a demand for thinner color filters to meet the needs for miniaturization and weight reduction of terminals. Therefore, the coloring agent used in the filter segment is sometimes required to have high coloring power.

In order to increase the contrast ratio, it is important to make the primary particles of the pigment contained in the color filter finer so that they are smaller than the wavelength of light, and to reduce the difference in refractive index between the pigment and the medium. be. Moreover, in order to increase the brightness of color liquid crystal displays, it is necessary to design a pigment composition having an optimum spectral shape. Therefore, if a pigment dispersant with high refining ability and dispersing ability can be used to refining and reliably dispersing a pigment having an appropriate spectral region, brightness and contrast ratio will be improved.

Conventionally, C.I., a diketopyrrolopyrrole pigment, has been used as a main pigment in the red filter segment of color filters. I. Pigment Red 254, and an anthraquinone pigment C.I. I. Pigment Red 177 is used alone or in combination.

Patent Documents 1 to 3 propose a pigment dispersant for refining the main pigment of the red filter segment. Although these pigment dispersants contribute to the improvement of the contrast ratio, they have a spectral shape different from that of the main pigment, so they have the problem of lowering brightness and coloring power. Therefore, there has been a demand for a pigment dispersant that satisfies all quality requirements to a high degree.

In recent years, as a new material, C.I. I. Pigment Red 176, C.I. I. Pigment Red 242, a monoazo pigment described in Patent Document 4, and a disazo pigment described in Patent Document 5 are proposed as main pigments. Although Patent Document 6 proposes a pigment dispersant corresponding to these problems, the above-mentioned problems cannot be solved.

JP 2007-79094 A JP 2007-314785 A WO 2011/052617 Pamphlet JP 2011-173971 A JP 2014-160160 A JP 2014-5439 A

The present invention has been made in view of such problems, and an object thereof is to provide a pigment dispersant that exhibits extremely excellent properties for improving the dispersibility of pigments. Furthermore, when a color filter is produced using a pigment composition or a coloring composition using it, the contrast ratio and brightness of the coating film (color filter) are highly compatible, and the high tinting strength also meets the needs of thin films. It is an object of the present invention to provide a pigment dispersant that meets these requirements.

The present inventors have made intensive studies to solve the above problems, and have found that a pigment dispersant having a specific structure can solve the above problems, resulting in the present invention.

That is, the present invention relates to a pigment dispersant represented by the following general formula (1).

General formula (1):

[In general formula (1), R1 to R5 are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxy group, or the following general formula (2), general formula (3) or general formula ( 4) and n is 1 or 2; At least one of R1 to R5 is a group represented by general formula (2), general formula (3) or general formula (4). ]

General formula (2):

[In general formula (2), m is an integer of 1 to 10, and R6 and R7 each independently represent an alkyl group. ]

General formula (3):

[In general formula (3), R8 is a group represented by general formula (5). R9 is a chlorine atom, a hydroxy group, or a group represented by general formula (5) or chemical formula (6). ]

General formula (4):

[In general formula (4), R10 to R14 are a hydrogen atom, an alkoxy group, or a group represented by general formula (2) or general formula (3), and at least one of R10 to R14 is represented by general formula ( 2) or a group represented by the general formula (3). ]

［一般式（５）中、ｊは１～１０の整数であり、Ｒ１５およびＲ１６はそれぞれ独立にアルキル基を表す。］ General formula (5):

[In general formula (5), j is an integer of 1 to 10, and R15 and R16 each independently represent an alkyl group. ]

Chemical formula (6):

In the present invention, R1 in general formula (1) represents a hydrogen atom, an alkyl group or an alkoxy group, R2 and R5 are hydrogen atoms, one of R3 or R4 is a hydrogen atom, and the other is a hydrogen atom, and the other is represented by the general formula ( 2) or the pigment dispersant which is a group represented by general formula (4).

The present invention also relates to the pigment dispersant, wherein n in formula (1) is 2.

The present invention also relates to a pigment composition containing the pigment dispersant and a pigment.

Further, according to the present invention, the pigment is C.I. I. Pigment Red 176, Pigment Red 177, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 269, C.I. I. Pigment Red 291, a red pigment represented by general formula (7), and a red pigment represented by general formula (8).

General formula (7):

[In general formula (7), R17 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a trifluoromethyl group, and R18 to R22 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a represents a fluoromethyl group and a -NHCONH- group; Adjacent groups of R18 to R22 may be linked by a -NHCONH- group to form a benzimidazolone ring. ]

General formula (8):

[In general formula (8), R represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a trifluoromethyl group, k is 1 or 2, and A is chemical formula (9), general formula (10) or It is a group represented by the general formula (11). ]

Chemical formula (9):

General formula (10):

[In general formula (10), R24 to R26 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group or an alkoxy group. ]

General formula (11):

[In general formula (11), B represents a direct bond or a divalent linking group. The divalent linking group includes an optionally substituted alkylene group, -O-, -S-, -CO-, -SO ₂ -, -COO-, -CONH-, and -SO ₂ NH-. show. ]

The present invention also relates to a coloring composition containing a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent contains the pigment composition.

The present invention also relates to the coloring composition, which further contains a photopolymerizable monomer.

The present invention also relates to a color filter comprising a filter segment formed from the coloring composition on a substrate.

The pigment dispersant of the present invention acts as a dispersant that contributes to improving the dispersibility of the pigment. A pigment composition or a coloring composition using it can provide a thin-film color filter with excellent contrast ratio and high brightness. In addition, the coloring composition of the present invention can also be used in industrial fields such as inkjet coloring compositions, printing inks, resin coloring agents, and paints.

Hereinafter, the coloring composition for color filters of the present invention will be described in detail. In this specification, when expressed as "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", a particular explanation "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless show. "C.I." means a color index (C.I.).

<Pigment Dispersant>
First, the pigment dispersant represented by formula (1) will be described.

General formula (1):

The pigment dispersant of the present invention is characterized by having an anthraquinone structure and a naphtholazo structure in its molecule. The above structures are related to the color development of organic dyes, and by linking them in a specific structure, they exhibit excellent pigment dispersibility through good interaction with pigments, resulting in high coloring power. I'm assuming that.

In the general formula (1), n is 1 or 2, and in the left parenthesis, any one or two of the hydrogen atoms on the anthraquinone are substituted with one or two amide nitrogen atoms It means that there is Preferably, n is 2, and any two of the hydrogen atoms on the anthraquinone are preferably substituted by the nitrogen atoms of two amides.

In general formula (1), R1 to R5 are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxy group, or the following general formula (2), general formula (3) or general formula (4) ) is a group represented by At least one of R1 to R5 is a group represented by general formula (2), general formula (3) or general formula (4).

Here, the "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a chlorine atom is preferable.

Further, the "alkyl group" includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group and octyl group. and alkyl groups having 1 to 8 carbon atoms such as 2-ethylhexyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

Examples of "alkoxy group" include alkoxy groups having 1 to 8 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, octyloxy group and tert-octyloxy group. Among these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is particularly preferable.

In addition, the "perfluoroalkyl group" includes perfluoro groups having 1 to 8 carbon atoms such as trifluoromethyl group, pentafluoroethyl group, hexafluoropropyl group, hexafluoroisopropyl group, nonafluorobutyl group, nonafluoroisobutyl group and the like. An alkyl group is mentioned. Among these, a perfluoroalkyl group having 1 to 4 carbon atoms is preferred, and a trifluoromethyl group or pentafluoroethyl group is more preferred.

General formula (2):

In general formula (2), m is an integer of 1 to 10, and R6 and R7 each independently represent an alkyl group.

General formula (3):

In general formula (3), R8 is a group represented by general formula (5). R9 is a chlorine atom, a hydroxy group, or a group represented by general formula (5) or chemical formula (6).

General formula (4):

In general formula (4), R10 to R14 are a hydrogen atom, an alkoxy group, or a group represented by general formula (2) or general formula (3), and at least one of R10 to R14 is represented by general formula (2 ) or a group represented by the general formula (3).

General formula (5):

In general formula (5), j is an integer of 1 to 10, and R15 and R16 each independently represent an alkyl group.

Chemical formula (6):

In general formula (1), R1 is preferably a hydrogen atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom, a methyl group, an ethyl group or a methoxy group. R2 and R5 are preferably hydrogen atoms, one of R3 or R4 is preferably a hydrogen atom, and the other is preferably a group represented by general formula (2) or general formula (4). More preferably, R3 or R4 is a group represented by general formula (4).

In general formula (2), m is preferably 1-4. Further, as the "alkyl group", the same ones as the "alkyl group" exemplified in the explanation of the general formula (1) can be mentioned, and the same ones are preferable.

In general formula (3), R9 is preferably a hydroxy group or a group represented by general formula (5) or chemical formula (6).

In general formula (4), the "alkoxy group" includes the same "alkoxy group" as exemplified in the explanation of general formula (1), and the same ones are preferred. Only one of R10 to R14 is a group represented by general formula (2), the rest are preferably hydrogen atoms, and only one of R11 to R13 is represented by general formula (2). group, and the remainder and R10 and R14 are more preferably hydrogen atoms.

In general formula (5), j is preferably 1-4. Further, as the "alkyl group", the same ones as the "alkyl group" exemplified in the explanation of the general formula (1) can be mentioned, and the same ones are preferable.

Particularly preferred embodiments of general formula (1) are shown below. n is 2, R1 is a hydrogen atom, a methyl group, an ethyl group, or a methoxy group, R2 and R5 are hydrogen atoms, one of R3 or R4 is a hydrogen atom, and the other is the general formula (4) is a group represented by In general formula (4), only one of R11 to R13 is a group represented by general formula (2), and the rest, R10 and R14 are hydrogen atoms.

The pigment dispersant may be mixed when dispersing the pigment, mixed in water or an organic solvent during production of the pigment composition, or added during salt milling. The amount of the pigment dispersant compounded is preferably in the range of 0.5 to 40 parts by mass with respect to 100 parts by mass of the pigment. More preferably, it is in the range of 1 to 35 parts by mass.

<Pigment composition>
The pigment composition of the present invention contains the pigment dispersant and a pigment.

<Pigment>
Next, the pigment used in the present invention will be explained. The pigment used in the present invention may be a pigment known in the industry, and may be an organic pigment or an inorganic pigment, but an organic pigment is preferred. Red organic pigments are preferred, and C.I. I. Pigment Red 176, Pigment Red 177, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 269, C.I. I. Pigment Red 291, a red pigment represented by general formula (7), or a red pigment represented by general formula (8).

General formula (7):

In general formula (7), R17 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group, and R18 to R22 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a trifluoro Represents a methyl group and -NHCONH- group. Adjacent groups of R18 to R22 may be linked by a -NHCONH- group to form a benzimidazolone ring.

Here, the "halogen atom", "alkyl group" and "alkoxy group" include those similar to the "halogen atom", "alkyl group" and "alkoxy group" exemplified in the explanation of the general formula (1). , and the like are preferred. More preferably, R17 is a hydrogen atom, a chlorine atom, a methoxy group, or a trifluoromethyl group. More preferably, R18 and R21 are each independently a chlorine atom, a methoxy group or a trifluoromethyl group, and R19, R20 and R22 are hydrogen atoms.

General formula (8):

In general formula (8), R23 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a trifluoromethyl group, k is 1 or 2, and A is chemical formula (9), general formula (10) or general It is a group represented by any one of the formulas (11).

Here, the "halogen atom", "alkyl group" and "alkoxy group" include those similar to the "halogen atom", "alkyl group" and "alkoxy group" exemplified in the explanation of the general formula (1). , and the like are preferred. More preferably, R23 is a hydrogen atom, a chlorine atom, a methoxy group, or a trifluoromethyl group. k is preferably 2, and A is more preferably general formula (9) or general formula (11).

Chemical formula (9):

General formula (10):

In general formula (10), R24 to R26 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group or an alkoxy group.

Here, the "halogen atom", "alkyl group" and "alkoxy group" include those similar to the "halogen atom", "alkyl group" and "alkoxy group" exemplified in the explanation of the general formula (1). , and the like are preferred. More preferably, each of R24 to R26 independently represents a hydrogen atom, a chlorine atom, a methyl group or a methoxy group.

General formula (11):

In general formula (11), B represents a direct bond or a divalent linking group. The divalent linking group includes an optionally substituted alkylene group, -O-, -S-, -CO-, -SO ₂ -, -COO-, -CONH-, and -SO ₂ NH-. show.

Here, the "alkylene group optionally having a substituent" includes methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, n-octylene group, n -dodecylene group, and substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, isobutyl group, tert-amyl group, 2-ethylhexyl group, and stearyl. group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like.

B is preferably an optionally substituted alkylene group, —O—, —S—, —CO—, or —SO ₂ —, with —SO ₂ — being particularly preferred.

Further, the pigment used in the pigment composition of the present invention is preferably finely divided. The method of refining is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation method can be used. etc., and can be miniaturized. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse in an organic solvent, and if it is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, the average primary particle size is more preferably in the range of 10 to 70 nm.

The pigment that can be used in the present invention preferably has a BET specific surface area of 70 m ² /g or more and 160 m ² /g or less, more preferably 80 m ² /g or more and less than 140 m ² /g, as determined by a nitrogen adsorption method. Particularly preferably, the specific surface area is 80 m ² /g or more and less than 120 m ² /g. When the specific surface area of the pigment is less ^than 70 m ² /g, the brightness and contrast ratio of the color filter may become low. Although the effect of improving the contrast ratio is observed, the dispersibility and dispersion stability of the pigment are low, so when a pigment dispersion is prepared using the pigment, the pigment particles reaggregate, resulting in high viscosity and instability. In some cases, the liquidity and storage stability become insufficient, and the luminance and contrast ratio characteristics of the color filter are extremely deteriorated. In addition, a large amount of the resin-type dispersant necessary for dispersion stabilization may be required, and since the resin-type dispersant is insoluble in the developer, the resolution and developability tend to decrease. can happen.

The measurement of the specific surface area of the pigment is the specific surface area of the dried pigment measured according to an automatic vapor adsorption measuring device (“BELSORP18” manufactured by Bell Japan Co., Ltd.) by the BET method of nitrogen adsorption.

<Coloring composition>
The coloring composition of the present invention contains a coloring agent, a binder resin, and an organic solvent, and if necessary, may also contain a photopolymerizable monomer, a dispersing aid, and a pigment other than the coloring agent. As the colorant, a pigment composition comprising a pigment dispersant represented by formula (1) and a pigment is used.

<Binder resin>
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include thermoplastic resins. When used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. Moreover, in order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali-developable colored resist material, the resin is three-dimensionally crosslinked when exposed to an active energy ray to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading of the colorant due to heat (deterioration of spectral characteristics) can be suppressed. It also has the effect of suppressing aggregation and precipitation of the colorant component in the development process.

The binder resin is preferably a resin having a spectral 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.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

When the binder resin is used as a photosensitive coloring composition for a color filter, a carboxyl group acting as a coloring agent adsorption group and an alkali-soluble group during development, an aliphatic group acting as an affinity group for the coloring agent carrier and solvent, and The balance of aromatic groups is important for colorant dispersibility, penetrability, developability and durability, and it is preferable to use a resin with an acid value of 20-300 mgKOH/g. A resin having an acid value within this range has excellent solubility in a developer and can form a fine pattern.

Since the binder resin has good film-forming properties and various resistances, it is preferably used in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant. Since it can be expressed, it is preferably used in an amount of 1000 parts by mass or less.

Examples of thermoplastic resins used as binder resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, and polyvinyl acetate. , polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Alkali-soluble vinyl resins obtained by copolymerizing ethylenically unsaturated monomers containing acidic groups include, for example, resins having acidic groups such as carboxyl groups and sulfone groups.
Specific examples of alkali-soluble resins include acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, or isobutylene/(anhydrous) maleic acid copolymer and the like. Among them, acrylic resins having acidic groups and at least one resin selected from styrene/styrenesulfonic acid copolymers, particularly acrylic resins having acidic groups are preferably used because of their high heat resistance and transparency.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenic double bonds are introduced by methods (i) and (ii) shown below.

[Method (i)]
As method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers. , The carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce it.

Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. Monocarboxylic acids and the like are mentioned, and these may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group and the like. Further, when tetrahydrophthalic anhydride or maleic anhydride having unsaturated ethylenic double bonds is used as the polybasic acid anhydride, the unsaturated ethylenic double bonds can be further increased.

As a method analogous to method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers There is a method of introducing an unsaturated ethylenic double bond and a carboxyl group by allowing an unsaturated ethylenic monomer having an epoxy group to undergo an addition reaction with a part of the carboxyl group.

[Method (ii)]
As method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and another unsaturated monobasic acid monomer having a carboxyl group or another monomer is copolymerized. There is a method of reacting the side chain hydroxyl groups of the resulting copolymer with the isocyanate groups of an unsaturated ethylenic monomer having an isocyanate group.

Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol (Meth)acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate can be mentioned, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone , and/or (poly)ester mono(meth)acrylates added with (poly)12-hydroxystearic acid and the like can also be used. 2-Hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred from the viewpoint of suppressing coating film foreign substances.

The unsaturated ethylenic monomer having an isocyanate group includes 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but is limited to these. Alternatively, two or more types can be used in combination.

<Organic solvent>
The coloring composition of the present invention is prepared by sufficiently dispersing and permeating a coloring agent in a coloring agent carrier, and coating it on a substrate such as a glass substrate so that the dry film thickness becomes 0.2 to 5 μm to form a filter segment. Contains organic solvents to facilitate cleaning. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of organic solvents include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1 ,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxypropionic acid ethyl, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene , o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol Dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, Cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipro pyrene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol Phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl Isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters and the like. These solvents may be used singly or as a mixture of two or more at any ratio as required.

The solvent can be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 5,000 parts by weight, based on 100 parts by weight of the coloring agent in the coloring composition.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the coloring composition of the present invention include monomers or oligomers that are cured by ultraviolet light, heat, or the like to form transparent resins.

Examples of monomers and oligomers that form transparent resins by curing with ultraviolet light or heat include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate (Meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, methylolated melamine Various acrylic and methacrylic esters such as (meth) acrylic esters, epoxy (meth) acrylates, urethane acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri vinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc., but not necessarily limited thereto. These photopolymerizable compounds can be used singly or as a mixture of two or more at an arbitrary ratio as required.

The content of the photopolymerizable monomer is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 400 parts by mass from the viewpoint of photocurability and developability. .

<Photoinitiator>
The coloring composition of the present invention is a solvent-developing or alkali-developing photosensitive coloring composition by adding a photopolymerization initiator in order to cure the composition by ultraviolet irradiation and form a filter segment by photolithography. can be prepared in the form

Photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 Acetophenone compounds such as -[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4' -methyldiphenyl sulfide or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 -diisopropylthioxanthone or thioxanthone compounds such as 2,4-diethylthioxanthone; 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(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, or 2,4- Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime )], or oxime ester compounds such as O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; bis(2,4,6- phosphine compounds such as trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole -based compounds; imidazole-based compounds; or titanocene-based compounds, etc. are used. These photopolymerization initiators can be used singly or as a mixture of two or more at an arbitrary ratio as required.

The content of the photopolymerization initiator is preferably 1 to 500 parts by mass, more preferably 5 to 400 parts by mass based on 100 parts by mass of the colorant, from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives and anthraquinone derivatives. , xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler ketone derivatives and the like. These sensitizers can be used singly or as a mixture of two or more at any ratio as required.

Further specific examples include Shin Okawara et al., "Dye Handbook" (1986, Kodansha), Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., "Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

Among the above sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability, 5 to 50 parts by weight. is more preferable.

<Polyfunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol. Polyfunctional thiols are compounds having two or more thiol (SH) groups. By using the polyfunctional thiol together with the above-mentioned photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. Polyfunctional aliphatic thiols in which SH groups are bonded to aliphatic groups such as methylene and ethylene groups are particularly preferred.

Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropio trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionate acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s - triazines and the like. These polyfunctional thiols can be used singly or as a mixture of two or more at any ratio as needed.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant.
Better development resistance can be obtained by using 0.05 parts by mass or more of the polyfunctional thiol. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Leveling agent>
A leveling agent is preferably added to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure in its main chain and a dimethylsiloxane having a polyester structure in its main chain can be used in combination. The content of the leveling agent is usually preferably from 0.003 to 1.0 parts by weight per 100 parts by weight of the total weight of the coloring composition.

Especially preferred as a leveling agent is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to the coloring composition, its It is useful that it has the characteristic of low surface tension lowering ability and good wettability to the glass plate despite the low surface tension lowering ability, and it is added in an amount that does not cause defects in the coating film due to bubbling. A substance capable of sufficiently suppressing chargeability can be preferably used. A dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used as a leveling agent having such preferred properties. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane is a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of dimethylpolysiloxane, a terminal modified type in which the terminal is bonded to the terminal of dimethylpolysiloxane, and a dimethylpolysiloxane. It may be of any linear block copolymer type with alternating repeating bonds. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but not limited to.

Anionic, cationic, nonionic, or amphoteric surfactants can be added to the leveling agent as auxiliaries. Two or more kinds of surfactants may be mixed and used. Examples of anionic surfactants added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and esters.

Cationic surfactants added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate. , polyethylene glycol monolaurate, and the like. Amphoteric surfactants added to the leveling agent include alkylbetaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline.

<Ultraviolet absorber, polymerization inhibitor>
The coloring composition of the present invention may contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

UV absorbers include, for example, 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, etc. hydroxyphenyltriazine series, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, Benzotriazoles such as 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2' , 4,4′-tetrahydroxybenzophenone and other benzophenones, phenyl salicylate, p-tert-butylphenyl salicylate and other salicylates, ethyl-2-cyano-3,3′-diphenyl acrylate and other cyanoacrylates system, 2,2,6,6-tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, poly [[6-[(1,1,3,3-tetrabutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl) imino] and other hindered amines. These ultraviolet absorbers can be used singly or as a mixture of two or more at an arbitrary ratio as required.

Examples of polymerization inhibitors include hydroquinones such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine and 3,7-dioctylphenothiazine, copper such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate and manganese diphenyldithiocarbamate and manganese salt compounds, nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine and their ammonium salts or aluminum salts. These polymerization inhibitors can be used singly or in combination of two or more at any ratio as required.

The ultraviolet absorber and polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the colorant in the coloring composition. Better resolution can be obtained by using 0.01 parts by mass or more of the ultraviolet absorber or the polymerization inhibitor.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant in order to increase the transmittance of the coating film. The antioxidant prevents the photopolymerization initiator contained in the coloring composition from being oxidized and yellowing due to the heat process during thermal curing or ITO annealing, so that the transmittance of the coating film can be increased. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and to obtain a high transmittance of the coating film.

Preferred antioxidants include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, sulfide-based antioxidants, and the like. More preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant. These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

Hindered phenol antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5- di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and the like.

Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N′-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4- piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4 -butane tetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6- Tetramethyl-4-piperidyl)imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4- diyl) {(2,2,6,6-tetramethyl-4-piperidyl)imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl)imino}], dimethyl succinate and 1-( 2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N- (1,2,2,6,6-Pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and the like.

As the phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin- 6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2- yl)oxy]ethyl]amine, ethylbis(2,4-ditert-butyl-6-methylphenyl)phosphite.

Sulfide antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]- o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like.

The content of the antioxidant is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total solid content of the coloring composition. If the amount of the antioxidant is less than 0.1 part by mass, the effect of increasing the transmittance is small, and if it is more than 5 parts by mass, the hardness is greatly reduced and the sensitivity of the coloring composition is greatly reduced.

<Other ingredients>
The colored composition of the present invention may contain an adhesion improving agent such as a silane coupling agent, or an amine-based compound that acts to reduce dissolved oxygen, in order to improve adhesion to a transparent substrate. can.

Examples of the silane coupling agent include vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane and vinyltrimethoxysilane, (meth)acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxy Epoxysilanes such as cyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ -aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-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, per 100 parts by weight of the colorant in the coloring composition.

Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-ethylhexyl-dimethylaminobenzoate, N,N-dimethyl p-toluidine and the like.

<Method for producing colored composition>
The coloring composition of the present invention is prepared by mixing a coloring agent in a coloring agent carrier such as a resin and/or a solvent, optionally together with a dispersing aid, using a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a It can be produced by finely dispersing it using various dispersing means such as a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be simultaneously dispersed in the colorant carrier, or separately dispersed in the colorant carrier may be mixed. The epoxy compound may be added at the stage of preparing the colorant dispersion, or may be added later to the prepared colorant dispersion to obtain the same effect. If the colorant such as dye has high solubility, specifically, if it has high solubility in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a photosensitive colored composition (resist material), it can be prepared as a solvent-developable or alkali-developable colored composition. The solvent-developable or alkali-developable coloring composition comprises the above-mentioned colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other pigment dispersants, and additives. etc. can be mixed and prepared. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersing aid>
When the colorant is dispersed in the colorant carrier, it is preferable to contain a dispersing aid such as a resin-type dispersant, a dye derivative, or a surfactant as appropriate. Since the dispersing aid has a great effect of preventing the re-aggregation of the colorant after dispersion, the colored composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid exhibits brightness and storage stability. get better.

<Resin Dispersant>
The resin-type dispersant has a colorant affinity site having a property of adsorbing to the colorant and a site compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant into the colorant carrier. It works to stabilize the Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and salts thereof Oily dispersants such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone Resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphoric acid esters, etc. are used, and these can be used alone or in combination of two or more. It is not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by BYK-Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE manufactured by Nippon Lubrizol Co., Ltd.-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 2410000, 240000 , 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-486, 486 manufactured by BASF, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824 etc.

Further, as the resin-type dispersant used in the present invention, those having an acidic substituent are preferable, and among them, those having an aromatic carboxyl group are preferable because they have a particularly large effect of preventing reaggregation of the colorant after dispersion. . As a resin type dispersant having an aromatic carboxyl group, one containing the following (S1) or (S2) is preferable.
(S1) A resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride.
(S2) a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride; A resin-type dispersant that is a coalesce.

[Resin Dispersant (S1)]
The resin-type dispersant (S1) can be produced by known methods such as those disclosed in WO2008/007776, JP-A-2008-029901, JP-A-2009-155406, and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a terminal hydroxyl group. For example, an ethylenically unsaturated monomer (r) is polymerized in the presence of a compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable to have a plurality of hydroxyl groups at the terminals, the compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, is obtained by adding a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) by polymerizing the ethylenically unsaturated monomer (r) contained. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of the tricarboxylic anhydride and/or the tetracarboxylic dianhydride to form an ester bond, while the anhydride ring is opened to form a carboxylic acid. produces

[Resin Dispersant (S2)]
The resin-type dispersant (S2) can be produced by known methods such as JP-A-2009-155406, JP-A-2010-185934, and JP-A-2011-157416. By polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product between a hydroxyl group of (q) and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride. can get. Above all, in the presence of a reaction product of a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride. Furthermore, it is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

(S1) and (S2) are the difference in whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. Although the molecular weight and the like may differ slightly depending on various conditions, theoretically the same product can be obtained if the raw materials and reaction conditions are the same.

The resin-type dispersant is preferably used in an amount of about 5 to 200 parts by mass, and more preferably in an amount of about 5 to 100 parts by mass based on the total amount of the coloring agent.

<Dye derivative>
The coloring composition of the present invention can contain a dye derivative. The pigment dispersant of the present invention is also classified as a pigment derivative, and if the content of other pigment derivatives is too high, the effect of the present invention may not be sufficiently exhibited. Therefore, the content of the other dye derivative is preferably less than that of the pigment dispersant of the present invention, and more preferably less than 50% by weight of the total amount of the pigment dispersant of the present invention and the other dye derivative combined. preferable.

As the dye derivative used in the present invention, known dye derivatives having an organic dye residue having an acidic group, a basic group, a neutral group, or the like can be used. For example, compounds having an acidic functional group such as a sulfo group, a carboxyl group, and a phosphoric acid group, amine salts thereof, compounds having a basic functional group such as a sulfonamide group or a tertiary amino group at the end, a phenyl group, and phthalimide Examples include compounds having neutral functional groups such as alkyl groups. Examples of organic dyes include diketopyrrolopyrrole pigments, copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, halogenated copper phthalocyanine, halogenated zinc phthalocyanine, halogenated aluminum phthalocyanine, phthalocyanine pigments such as metal-free phthalocyanine, aminoanthraquinone, diamino Anthraquinone pigments such as dianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo, disazo, polyazo, etc. azo pigments, and the like.
More specifically, JP-A-61-246261, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-1999 11-199796, JP 2001-172520, JP 2001-220520, JP 2002-201377, JP 2003-165922, JP 2003-168208, JP 2003- 171594, JP 2004-217842, JP 2005-213404, JP 2006-291194, JP 2007-079094, JP 2007-226161, JP 2007-314681 Publications, JP 2007-314785, JP 2008-31281, JP 2009-57478, WO2009/025325, WO2009/081930, JP 2011-162662, WO2011/052617 Pamphlet, JP 2012-172092, JP 2012-208329, JP 2012-226110, WO2012/102399, JP 2014-5439, WO2016/163351, JP 2017- 156397, Japanese Patent No. 5753266, and the like, and these can be used alone or in combination of two or more. In these documents, dye derivatives are sometimes described as derivatives, pigment derivatives, pigment dispersants, or simply compounds. is synonymous with a dye derivative.

Among the dye derivatives used in the present invention, a dye derivative having a basic substituent is preferable because the effect of suppressing aggregation between pigments is remarkable. Furthermore, as the organic dye residue, those derived from diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinophthalone-based pigments, and azo-based pigments are preferable from the viewpoint of hue and contrast.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate. , monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; Although they can be mixed and used, they are not necessarily limited to these.

When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant. If the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by mass, the excess dispersant may affect dispersion. .

<Removal of coarse particles>
The colored composition of the present invention is separated by means of centrifugation, filtration with a sintered filter, membrane filter, or the like, and the coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more of coarse particles and It is preferable to remove mixed dust. Thus, the coloring composition preferably does not substantially contain particles of 0.5 μm or larger. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be explained. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment on a substrate, and further comprises a magenta filter segment, a cyan filter segment, or a yellow filter segment. and the at least one filter segment is formed from the coloring composition of the present invention.

<Manufacturing method of color filter>
The color filter of the invention can be produced by a printing method or a photolithographic method. Formation of filter segments by a printing method can be patterned simply by repeating printing and drying of a coloring composition prepared as a printing ink, and therefore, as a method for producing color filters, it is low cost and excellent in mass productivity. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the viscosity of the ink using a dispersant or an extender.

When the filter segment is formed by photolithography, the colored composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto the transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact or non-contact with this film. After that, the film is immersed in a solvent or alkaline developer or sprayed with a developer to remove the uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to promote polymerization of the colored resist material, heating may be applied as necessary. According to the photolithography method, it is possible to manufacture a color filter with higher precision than the printing method.

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

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method, etc. in addition to the above methods, and the colored composition of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which filter segments are formed in advance on the surface of a removable transfer base sheet, and the filter segments are transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate. Examples of the black matrix include, but are not limited to, chromium or chromium/chromium oxide multilayer films, inorganic films such as titanium nitride, and resin films in which a light shielding agent is dispersed. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or reflective substrate, and then each color filter segment may be formed. An overcoat film, a transparent conductive film, and the like are formed on the color filter of the present invention, if necessary.

The dry film thickness of the filter segment and black matrix is preferably 0.2-10 μm, more preferably 0.2-5 μm. A vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used to dry the coating film.

The color filter is attached to the opposing substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed. A liquid crystal display panel is manufactured by laminating them together.

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

As the transparent substrate, glass plates such as soda lime glass, low-alkali borosilicate glass, alkali-free aluminoborosilicate glass, etc., and resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. are used. 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 for driving the liquid crystal after panelization.

EXAMPLES The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, "parts" and "%" represent "mass parts" and "mass%" respectively. Me represents a methyl group, Et represents an ethyl group, and n-Bu represents a normal butyl group. "PGMAc" means propylene glycol monomethyl ether acetate.

<Resin weight average molecular weight (Mw), number average molecular weight (Mn),>
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resins were determined by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as an apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40. °C, a THF solution was used as an eluent, and the flow rate was 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalent values.

<Acid value of resin (mgKOH/g)>
Add 80 ml of acetone and 10 ml of water to 0.5 to 1.0 g of the resin solution and stir to dissolve uniformly. Sangyo Co., Ltd.) was used to measure the acid value of the resin solution. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Method for identifying pigment dispersant>
When identifying the pigment dispersant of the present invention, a MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker-Daltonics Co., Ltd. is used, and the molecular ion peak of the mass spectrum obtained and the mass obtained by calculation It was identified by agreement with the numbers, and further, by using a Perkin-Elmer 2400 CHN Element Analyzer, the ratio of each element obtained and agreement with the theoretical values.

<Average primary particle size of pigment>
The average primary particle size of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating a cube with the obtained particle size, and the volume average particle size was taken as the average primary particle size.

First, methods for producing acrylic resin solutions and resin-type dispersant solutions used in Examples, Production Examples, and Comparative Examples will be described.

<Method for producing acrylic resin solution>
(Preparation of acrylic resin solution [AR-1])
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, the mixture was added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd. "Aronix M110") 20.7 and 1.1 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. to prepare an acrylic resin solution [AR-1]. The weight average molecular weight (Mw) was 26,000.

(Preparation of acrylic resin solution [AR-2])
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI, 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. to prepare an acrylic resin solution [AR-2]. The weight average molecular weight (Mw) was 18,000.

<Method for producing resin-type dispersant solution>
(Preparation of resin type dispersant solution [PD-1])
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, and 20 parts of benzyl methacrylate were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 50° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted. 19 parts of pyromellitic anhydride, 297 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100° C. for 7 hours. . After confirming that 98% or more of the acid anhydride was half-esterified by acid value measurement, the reaction was terminated to obtain a resin-type dispersant having an acid value of 70 mgKOH/g and a weight average molecular weight (Mw) of 8,500. PGMAc was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution [PD-1].

(Preparation of resin type dispersant solution [PD-2])
10 parts of methacrylic acid, 140 parts of methyl methacrylate, 30 parts of benzyl methacrylate, and 20 parts of cyclohexyl acrylate were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 50° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted. 35 parts of trimellitic anhydride, 370 parts of PGMAc, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100° C. for 7 hours. Acid value measurement confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a resin type dispersant having an acid value of 109 mgKOH/g and a weight average molecular weight (Mw) of 8,500. PGMAc was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution [PD-2].

(Preparation of resin type dispersant solution [PD-3])
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, 6.0 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic anhydride, mono-n-butyl tin (IV ) 0.01 part of oxide and 23.5 parts of cyclohexanone were charged and purged with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 97% or more of the acid anhydride is half-esterified by acid value measurement, the temperature in the system is cooled to 70°C, 80 parts of methyl methacrylate and 20.0 parts of hydroxyethyl methacrylate are charged, A solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 26.2 parts of cyclohexanone was added and reacted for 10 hours. After confirming that the polymerization had progressed by 95% by measuring the solid content, the reaction was terminated to obtain a resin-type dispersant having an acid value of 43 mgKOH/g and a weight average molecular weight (Mw) of 9,500. PGMAc was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution [PD-3].

(Preparation of resin type dispersant solution [PD-4])
80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (manufactured by Showa Denko), ETERNACOLL OXMA (Ube Kosan Co., Ltd.) and 100 parts of PGMAc were charged, and the contents were replaced with nitrogen gas. The inside of the reaction vessel is heated to 80° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added. and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Next, BPAF: 39 parts of 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N (Hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.)) 106 parts, trimellitic anhydride 33 parts, cyclohexanone 392 parts, 1,8-diazabicyclo-[5.4.0]-7-undecene 0.40 as a catalyst parts were added and reacted at 100° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The solid content was adjusted to 40% with PGMAc to obtain a resin-type dispersant having an acid value of 94 mgKOH/g and a weight average molecular weight (Mw) of 25,000. PGMAc was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution [PD-4].

<Method for producing pigment dispersant>
Table 1 shows the base compounds ([B-1] to [B-7]) used this time.

The method for producing the base compound can be carried out with reference to known methods such as Example 1 of Japanese Patent No. 5316690, for example.

Next, the method for producing the coupler compound used this time will be described.

(Production of coupler compound [C-1])

After mixing 167 parts of 3-hydroxy-2-naphthoic acid, 1500 parts of tetrahydrofuran and 1 part of N,N-dimethylformamide, 221 parts of thionyl chloride was added and stirred for 1 hour at room temperature to obtain a carboxylic acid chloride solution. Obtained. Separately, a solution was prepared by mixing 1000 parts of N-methylpyrrolidone and 105 parts of 2,6-diaminoanthraquinone, and the carboxylic acid chloride solution was added dropwise to this solution over 30 minutes. At this time, the dropwise addition was performed while maintaining the temperature of the reaction solution at 10° C. or lower. After the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours, and the precipitated reaction product was collected by filtration to obtain the desired product. Further, by washing with 1000 parts of methanol and drying under reduced pressure, 249 parts of coupler compound [C-1] was obtained (yield 97.8%).

(Production of coupler compound [C-2])
The same procedure as in the production of coupler compound [C-1] was performed except that 105 parts of 1,5-diaminoanthraquinone was used instead of 105 parts of 2,6-diaminoanthraquinone used in the production of coupler compound [C-1]. The operation was carried out to obtain 248 parts of coupler compound [C-2] (yield 97.5%).

(Production of coupler compound [C-3])
The same procedure as in the production of coupler compound [C-1] was performed except that 105 parts of 1,4-diaminoanthraquinone was used instead of 105 parts of 2,6-diaminoanthraquinone used in the production of coupler compound [C-1]. The operation was carried out to obtain 245 parts of coupler compound [C-3] (yield 96.2%).

(Production of coupler compound [C-4])
The same operation as in the production of coupler compound [C-1] was performed except that 197 parts of 1-aminoanthraquinone was used instead of 105 parts of 2,6-diaminoanthraquinone used in the production of coupler compound [C-1]. 340 parts of the coupler compound [C-4] (yield 97.7%) was obtained.

(Production of coupler compound [C-5])
The same operation as in the production of coupler compound [C-1] was performed except that 197 parts of 2-aminoanthraquinone was used instead of 105 parts of 2,6-diaminoanthraquinone used in the production of coupler compound [C-1]. 341 parts of the coupler compound [C-5] (yield 98.0%) was obtained.

N－メチルピロリドン１５００部にベース化合物［Ｂ－１］１８５部を加えた後、３５％塩酸２９４部を加え、－２～０℃になるよう冷却した。この溶液に２５％亜硝酸ナトリウム水溶液２０８部を加えた後、０～５℃に保持しながら、３０分間攪拌し、ジアゾニウム溶液を調製した。別途、カップラー化合物［Ｃ－１］２１６部と、２５％水酸化ナトリウム溶液３１６部、メタノール１５００部からなるカップラー溶液を調製した。調製したジアゾニウム溶液とカップラー溶液を、同時にｐＨ５．４の酢酸バッファー溶液１０００部に１０分間で滴下した。滴下終了後、室温で３０分間攪拌した後、さらに、８０℃に保持しながら攪拌し、析出した反応物をろ取し、熱湯で洗浄後、乾燥して顔料分散剤［Ｄ－１］を３８６部得た。ＴＯＦ－ＭＳによる質量分析および元素分析の結果、顔料分散剤［Ｄ－１］であることを同定した。 [Example 1]
(Production of pigment dispersant [D-1])

After adding 185 parts of base compound [B-1] to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added and the mixture was cooled to -2 to 0°C. After adding 208 parts of a 25% sodium nitrite aqueous solution to this solution, the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5°C to prepare a diazonium solution. Separately, a coupler solution comprising 216 parts of coupler compound [C-1], 316 parts of 25% sodium hydroxide solution and 1500 parts of methanol was prepared. The prepared diazonium solution and coupler solution were simultaneously added dropwise to 1000 parts of an acetate buffer solution of pH 5.4 over 10 minutes. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes, and further stirred while the temperature was kept at 80°C. I got it. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as the pigment dispersant [D-1].

Pigment dispersant [D-1]:

[Example 2]
(Production of pigment dispersant [D-2])
Instead of 185 parts of the base compound [B-1] used in the production of the pigment dispersant [D-1], except that 252 parts of the base compound [B-2] were used. 446 parts of a pigment dispersant [D-2] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as the pigment dispersant [D-2].

Pigment dispersant [D-2]:

[Example 3]
(Production of pigment dispersant [D-3])
Instead of 185 parts of the base compound [B-1] used in the production of the pigment dispersant [D-1], except for using 263 parts of the base compound [B-3], the pigment dispersant [D-1] 457 parts of a pigment dispersant [D-3] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as the pigment dispersant [D-3].

Pigment dispersant [D-3]:

[Example 4]
(Production of pigment dispersant [D-4])
90 parts of 80% acetic acid was added to 634 parts of water and cooled to 5-10°C. 149 parts of cyanuric chloride and 112 parts of 3-aminoacetanilide were added and stirred at 10 to 20° C. for 1 hour. Next, 1314 parts of a 2.5% NaOH aqueous solution was added dropwise, and the mixture was further stirred at 10 to 20°C for 1 hour. Subsequently, 97 parts of diethylaminopropylamine was added, and the mixture was stirred at room temperature for 1 hour. After cooling to 5 to 10°C, 1314 parts of a 2.5% NaOH aqueous solution was added dropwise, followed by stirring at 75°C for 2 hours. After allowing to cool, 387 parts of a 35% HCl aqueous solution was added, stirred at 100°C for 3 hours, and allowed to cool. Ice was added to the above solution to adjust the temperature to 5° C. An aqueous solution prepared by adding 54 parts of sodium nitrite to 180 parts of water was added and stirred for 2 hours. Subsequently, an aqueous solution consisting of 550 parts of an 80% aqueous acetic acid solution, 600 parts of a 25% aqueous sodium hydroxide solution, and 650 parts of water was added to obtain an aqueous diazonium salt solution. Separately, a coupler solution comprising 216 parts of coupler compound [C-1], 316 parts of 25% sodium hydroxide solution and 1500 parts of methanol was prepared. This coupler solution was injected into the diazonium salt aqueous solution at 5° C. over 30 minutes to carry out a coupling reaction. The pH at this time was 4.6. After the completion of dropping, the mixture was stirred at room temperature for 30 minutes, and further stirred while the temperature was kept at 80°C. I got it. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as the pigment dispersant [D-4].

Pigment dispersant [D-4]:

[Example 5]
(Production of pigment dispersant [D-5])
Instead of 97 parts of diethylaminopropylamine used in the production of pigment dispersant [D-4], the same operation as in the production of pigment dispersant [D-4] was performed, except that 164 parts of dimethylaminoethylamine was used. 477 parts of pigment dispersant [D-5] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as a pigment dispersant [D-5].

Pigment dispersant [D-5]:

[Example 6]
(Production of pigment dispersant [D-6])
Instead of 185 parts of the base compound [B-1] used in the production of the pigment dispersant [D-1], except for using 330 parts of the base compound [B-4], the pigment dispersant [D-1] 510 parts of a pigment dispersant [D-6] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-6].

Pigment dispersant [D-6]:

[Example 7]
(Production of pigment dispersant [D-7])
Instead of 185 parts of the base compound [B-1] used in the production of the pigment dispersant [D-1], except for using 299 parts of the base compound [B-5], the pigment dispersant [D-1] 491 parts of a pigment dispersant [D-7] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-7].

Pigment dispersant [D-7]:

[Example 8]
(Production of pigment dispersant [D-8])
Instead of 185 parts of the base compound [B-1] used in the production of the pigment dispersant [D-1], except for using 354 parts of the base compound [B-6], the pigment dispersant [D-1] 542 parts of a pigment dispersant [D-8] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-8].

Pigment dispersant [D-8]:

[Example 9]
(Production of pigment dispersant [D-9])
Instead of 185 parts of the base compound [B-1] used in the production of the pigment dispersant [D-1], except for using 484 parts of the base compound [B-7], the pigment dispersant [D-1] 659 parts of a pigment dispersant [D-9] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-9].

Pigment dispersant [D-9]:

[Example 10]
(Production of pigment dispersant [D-10])
Instead of 216 parts of the coupler compound [C-1] used in the production of the pigment dispersant [D-7], 216 parts of the coupler compound [C-2] were used. 490 parts of a pigment dispersant [D-10] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-10].

Pigment dispersant [D-10]:

[Example 11]
(Production of pigment dispersant [D-11])
Instead of 216 parts of the coupler compound [C-1] used in the production of the pigment dispersant [D-7], 216 parts of the coupler compound [C-3] were used. 488 parts of a pigment dispersant [D-11] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-11].

Pigment dispersant [D-11]:

[Example 12]
(Production of pigment dispersant [D-12])
Instead of 216 parts of the coupler compound [C-1] used in the production of the pigment dispersant [D-1], 147 parts of the coupler compound [C-4] were used. 229 parts of a pigment dispersant [D-12] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-12].

Pigment dispersant [D-12]:

[Example 13]
(Production of pigment dispersant [D-13])
Manufacture of pigment dispersant [D-7] except that 147 parts of coupler compound [C-4] was used instead of 216 parts of coupler compound [C-1] used in the manufacture of pigment dispersant [D-7] 283 parts of a pigment dispersant [D-13] was obtained by performing the same operation. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-13].

Pigment dispersant [D-13]:

[Example 14]
(Production of pigment dispersant [D-14])
Instead of 216 parts of the coupler compound [C-1] used in the production of the pigment dispersant [D-7], except that 147 parts of the coupler compound [C-5] were used. 281 parts of a pigment dispersant [D-14] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-14].

Pigment dispersant [D-14]:

[Example 15]
(Production of pigment dispersant [D-15])
Instead of 216 parts of the coupler compound [C-1] used in the production of the pigment dispersant [D-9], except that 147 parts of the coupler compound [C-5] were used. 309 parts of a pigment dispersant [D-15] was obtained by performing the same operation as in the production. As a result of TOF-MS mass spectrometry and elemental analysis, it was identified as a pigment dispersant [D-15].

Pigment dispersant [D-15]:

<Method for producing dye derivative>
The manufacturing method and structure of the dye derivative used in the comparative example are shown.

(Production of dye derivative [E-1])
A dye derivative [E-1] was produced with reference to Example 1 of Japanese Patent No. 5316690.

Dye derivative [E-1]:

(Production of dye derivative [E-2])
With reference to Production Example 11 of Japanese Patent No. 1548321, dye derivative [E-2] was produced.

Dye derivative [E-2]:

<Method for producing pigment>
The commercially available pigments used this time are listed.
C. I. Pigment Red 176: manufactured by CLARIANT
"Graphtol Carmine HF3C"
Abbreviated as PR176 HF3C.
C. I. Pigment Red 177: manufactured by CINIC
"Cinilex Red SR3C"
Abbreviated as PR177 SR3C.
C. I. Pigment Red 242: manufactured by Clariant
"PV Fast Scarlet 4RF"
Abbreviated as PR242 4RF.
C. I. Pigment Red 254: manufactured by CINIC
"Cinilex DPP Red ST"
Abbreviated as PR254 ST.
C. I. Pigment Red 269: manufactured by Sanyo Pigment Co., Ltd.
"Permanent Carmine 3810"
Abbreviated as PR269 3810.

(Production of C.I. Pigment Red 291)
200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube under a nitrogen atmosphere, and the mixture was heated to 100° C. with stirring to form an alcoholate solution. prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90° C. with stirring to prepare a solution of their mixture. The heated solution of this mixture was slowly added dropwise at a constant rate over 2 hours into the above alcoholate solution heated to 100° C. with vigorous stirring. After the dropwise addition was completed, heating and stirring were continued at 90° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a jacketed glass reaction vessel and cooled to -10°C. While the cooled mixture was rotated using a high-speed stirring disperser, the diketopyrrolopyrrole-based compound alkali metal salt solution previously obtained, which had been cooled to 75° C., was added little by little. At this time, while cooling with a refrigerant so that the temperature of the mixture consisting of methanol, acetic acid, and water is always kept at -5 ° C. or lower, and the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. was added in small portions over approximately 120 minutes, adjusting the rate of addition of . After addition of the alkali metal salt, red crystals precipitated to form a red suspension. After vigorously stirring this suspension for 10 minutes, it was filtered using a Nutsche, and then 300 parts of methanol cooled to 10° C. and 1000 parts of water were sprinkled over and washed. Subsequently, this water paste of coarse crystals was subjected to heat treatment at 80° C. for 24 hours using a vacuum dryer, and dried until the water content became less than 1% by weight. Then, it is pulverized with a hammer mill type pulverizer and passed through a 5 mm screen to obtain a C.I. I. Pigment Red 291 is obtained. Abbreviated as PR291.

C. I. Pigment Red 291:

(Production of azo pigment [A-1])
125 parts of 3-amino-4-methoxybenzanilide is dispersed in 2000 parts of water, ice is added to adjust the temperature to 5° C., 205 parts of 35% hydrochloric acid aqueous solution is added, and after stirring for 1 hour, 37.5 parts of sodium nitrite. 110 parts of water to prepare an aqueous solution, and the mixture was stirred for 2 hours. An aqueous solution consisting of 380 parts of an 80% aqueous acetic acid solution, 418 parts of a 25% aqueous sodium hydroxide solution, and 413 parts of water was added to prepare an aqueous diazonium salt solution. On the other hand, 189 parts of N-[2-chloro-5-trifluoromethylphenyl]-3-hydroxy-2-naphthalenecarboxamide and 1344 parts of 25% aqueous sodium hydroxide solution were dissolved in 3500 parts of methanol to prepare a coupler solution. This coupler solution was injected into the diazonium salt aqueous solution at 5° C. over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70° C., filtered, washed with water, and dried at 90° C. for 24 hours to obtain 307 parts of azo pigment [A-1]. As a result of mass spectrometry by TOF-MS, it was identified as the azo pigment [A-1].

Azo pigment [A-1]:

(Production of azo pigment [A-2])
After adding 181 parts of 3-amino-4-methoxybenzanilide to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added and the mixture was cooled to -2 to 0°C. After adding 208 parts of a 25% sodium nitrite aqueous solution to this solution, the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5°C to prepare a diazonium solution. Separately, a coupler solution comprising 216 parts of coupler compound [C-1], 316 parts of 25% sodium hydroxide solution and 1500 parts of methanol was prepared. The prepared diazonium solution and coupler solution were simultaneously added dropwise to 1000 parts of an acetate buffer solution of pH 5.4 over 10 minutes. After completion of dropping, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining the temperature at 80°C. The precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 386 parts of the azo pigment [A-2]. Obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment [A-2].

Azo pigment [A-2]:

(Production of azo pigment [A-3])
After adding 200 parts of 2-hydroxy-3-naphthoic acid to 1500 parts of tetrahydrofuran (THF), 164 parts of thionyl chloride was added and stirred at room temperature for 2 hours to prepare a 2-hydroxy-3-naphthoic acid chloride solution. Separately, after adding 85 parts of 2,5-dichloro-1,4-phenylenediamine to 1500 parts of tetrahydrofuran (THF), the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5°C. The prepared 2-hydroxy-3-naphthoic acid chloride solution was added dropwise thereto over 30 minutes, and after dropping, the mixture was stirred at room temperature for 2 hours. After adding 3000 parts of warm water, the precipitated product was filtered and tetrahydrofuran (THF) was washed with hot water. The wet cake taken out was dried to obtain 230 parts of the coupler compound [C-6] (yield: 93.2%).

After adding 181 parts of 3-amino-4-methoxybenzanilide to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added and the mixture was cooled to -2 to 0°C. After adding 208 parts of a 25% sodium nitrite aqueous solution to this solution, the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5°C to prepare a diazonium solution. Separately, a coupler solution comprising 193 parts of the coupler compound [C-6], 316 parts of a 25% sodium hydroxide solution and 1500 parts of methanol was prepared. The prepared diazonium solution and coupler solution were simultaneously added dropwise to 1000 parts of an acetate buffer solution of pH 5.4 over 10 minutes. After the completion of dropping, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining the temperature at 80°C. The precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 363 parts of the azo pigment [A-3]. Obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as an azo pigment [A-3].

Azo pigment [A-3]:

(Production of azo pigment [A-4])
After adding 200 parts of 2-hydroxy-3-naphthoic acid to 1500 parts of tetrahydrofuran (THF), 164 parts of thionyl chloride was added and stirred at room temperature for 2 hours to prepare a 2-hydroxy-3-naphthoic acid chloride solution. Separately, 119 parts of 3,3′-diaminodiphenylsulfone was added to 1500 parts of tetrahydrofuran (THF), and the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5°C. The prepared 2-hydroxy-3-naphthoic acid chloride solution was added dropwise thereto over 30 minutes, and after dropping, the mixture was stirred at room temperature for 2 hours. After adding 3000 parts of warm water, the precipitated product was filtered and tetrahydrofuran (THF) was washed with hot water. The wet cake taken out was dried to obtain 260 parts of the coupler compound [C-7] (yield: 92.9%).

After adding 181 parts of 3-amino-4-methoxybenzanilide to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added and the mixture was cooled to -2 to 0°C. After adding 208 parts of a 25% sodium nitrite aqueous solution to this solution, the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5°C to prepare a diazonium solution. Separately, a coupler solution comprising 219 parts of coupler compound [C-7], 316 parts of 25% sodium hydroxide solution and 1500 parts of methanol was prepared. The prepared diazonium solution and coupler solution were simultaneously added dropwise to 1000 parts of an acetate buffer solution of pH 5.4 over 10 minutes. After the completion of dropping, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining the temperature at 80°C. The precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 388 parts of the azo pigment [A-4]. Obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as an azo pigment [A-4].

Azo pigment [A-4]:

<Method for producing pigment composition>
[Example 16]
(Production of pigment composition [P-1])
90 parts of PR242 4RF, 10 parts of pigment dispersant [D-7], 1000 parts of sodium chloride, and 100 parts of diethylene glycol (hereinafter abbreviated as DEG) were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated to 70°C. and kneaded for 8 hours to obtain a mixture. Each of the obtained mixtures was added to 10,000 parts of water, stirred for 1 hour with a high-speed mixer while being heated to 40±5° C. to form a slurry, filtered, and added to 10,000 parts of water at 40±5° C. It was washed to remove sodium chloride and DEG, and dried at 90°C to obtain a pigment composition [P-1].

[Example 17] to [Example 22]
(Production of Pigment Compositions [P-2] to [P-7])
Pigment compositions [P-2] to [P-7] were obtained in the same manner as for pigment composition [P-1], except that the compositions were changed to those shown in Table 2.

[Comparative Example 1]
(Production of pigment composition [P-8])
100 parts of PR242 4RF, 1000 parts of sodium chloride, and 100 parts of diethylene glycol (hereinafter abbreviated as DEG) were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 8 hours to obtain a mixture. Each of the obtained mixtures was added to 10,000 parts of water, stirred for 1 hour with a high-speed mixer while being heated to 40±5° C. to form a slurry, filtered, and added to 10,000 parts of water at 40±5° C. It was washed to remove sodium chloride and DEG, and dried at 90°C to obtain a pigment composition [P-8].

[Comparative Example 2] to [Comparative Example 5]
(Production of Pigment Compositions [P-9] to [P-12])
Pigment compositions [P-9] to [P-12] were obtained in the same manner as for pigment composition [P-8] except that the composition was changed to that shown in Table 2.

[Comparative Example 6]
(Production of pigment composition [P-13])
90 parts of PR242 4RF, 10 parts of dye derivative [E-1], 1000 parts of sodium chloride, and 100 parts of DEG were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 8 hours to obtain a mixture. rice field. Each of the obtained mixtures was added to 10,000 parts of water, stirred for 1 hour with a high-speed mixer while being heated to 40±5° C. to form a slurry, filtered, and added to 10,000 parts of water at 40±5° C. It was washed to remove sodium chloride and DEG, and dried at 90°C to obtain a pigment composition [P-13].

[Comparative Example 7], [Comparative Example 8]
(Production of Pigment Compositions [P-14] and [P-15])
Pigment compositions [P-14] and [P-15] were obtained in the same manner as the pigment composition [P-13] except that the composition was changed to that shown in Table 2.

<Method for producing colored composition>
[Example 23]
(Preparation of coloring composition [CP-1])
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size is 5.5 mm. The mixture was filtered through a 0 μm filter to obtain a coloring composition [CP-1] having a nonvolatile content of 15%.
PR242 4RF: 8.1 parts Pigment dispersant [D-1]: 0.9 parts Acrylic resin solution [AR-1]: 6.0 parts Resin type dispersant solution [PD-1]: 12.0 parts PGMAc: 73.0 parts

[Example 24] to [Example 57]
(Production of colored compositions [CP-2] to [CP-35])
Colored compositions [CP-2] to [CP-35] were obtained in the same manner as the colored composition [CP-1] except that the compositions were changed to those shown in Table 3.

[Comparative Example 9]
(Production of coloring composition [CP-36])
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size is 5.5 mm. Filtration through a 0 μm filter gave a colored composition [CP-36] having a non-volatile content of 15%.
PR242 4RF: 9.0 parts Acrylic resin solution [AR-1]: 6.0 parts Resin type dispersant solution [PD-1]: 12.0 parts PGMAc: 73.0 parts

[Comparative Example 10] to [Comparative Example 18]
(Production of colored compositions [CP-37] to [CP-45])
Colored compositions [CP-37] to [CP-45] were obtained in the same manner as the colored composition [CP-36] except that the composition was changed to that shown in Table 3.

[Comparative Example 19]
(Production of coloring composition [CP-46])
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size is 5.5 mm. Filtration through a 0 μm filter gave a colored composition [CP-46] with a nonvolatile content of 15%.
PR242 4RF: 8.1 parts Dye derivative [E-1]: 0.9 parts Acrylic resin solution [AR-1]: 6.0 parts Resin type dispersant solution [PD-1]: 12.0 parts PGMAc: 73 parts .0 copies

[Comparative Example 20] to [Comparative Example 28]
(Production of colored compositions [CP-47] to [CP-55])
Coloring compositions [CP-47] to [CP-55] were obtained in the same manner as the coloring composition [CP-46] except that the composition was changed to that shown in Table 3.

[Example 58]
(Preparation of coloring composition [CP-56])
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size is 5.5 mm. Filtration through a 0 μm filter gave a colored composition [CP-56] with a nonvolatile content of 15%.
Pigment composition [P-1]: 9.0 parts Acrylic resin solution [AR-1]: 6.0 parts Resin type dispersant solution [PD-1]: 12.0 parts PGMAc: 73.0 parts

[Example 59] to [Example 64], [Comparative Example 29] to [Comparative Example 36]
(Production of colored compositions [CP-57] to [CP-70])
Coloring compositions [CP-57] to [CP-70] were obtained in the same manner as the coloring composition [CP-56] except that the composition was changed to that shown in Table 4.

<Evaluation of coloring composition>
The initial viscosity and storage stability of the obtained colored composition were measured by the following methods. Evaluation results are shown in Tables 3 and 4.

(Initial viscosity evaluation)
The viscosity of the coloring composition, immediately after preparing the coloring composition, at 25 ° C., using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm (initial viscosity) was measured. . Evaluation was made in the following three stages.
○: less than 20.0 [mPa s] (good)
△: 20.0 or more to less than 40.0 [mPa s] (defective)
×: 40.0 or more [mPa s] (extremely poor)

(Storage stability evaluation)
The colored composition is stored in a constant temperature room at 40 ° C. for 7 days, and the viscosity measured after that is compared with the initial viscosity, the viscosity change rate (%) (= (viscosity after storage at 40 ° C. for 7 days - initial viscosity )/initial viscosity×100) was calculated, and storage stability was evaluated according to the following criteria.
◎: Viscosity change rate is less than 10% (extremely good)
○: Viscosity change rate is 10% or more and less than 20% (good)
△: Viscosity change rate is 20% or more and less than 50% (defective)
×: Viscosity change rate is 50% or more (extremely poor)

As shown in Tables 3 and 4, the coloring composition using the pigment dispersant of the present invention had good results in terms of initial viscosity and storage stability.

<Method for producing a photosensitive coloring composition>
[Example 65]
(Preparation of photosensitive coloring composition [CR-1])
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition (CR-1).
Coloring composition [CP-1] 20.6 parts Coloring composition [CP-53] 22.4 parts Acrylic resin solution [AR-2] 8.2 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Aronix M402 ”) 2.8 parts Photopolymerization initiator (manufactured by BASF “Irgacure 907”) 2.0 parts Sensitizer (manufactured by Hodogaya Chemical Co., Ltd. “EAB-F”) 0.4 parts PGMAc 43.6 parts

[Example 66] to [Example 106], [Comparative Example 37] to [Comparative Example 63]
(Preparation of photosensitive coloring compositions [CR-2] to [CR-69])
Except for changing the coloring composition [CP-1] and the coloring composition [CP-53] to the combination and ratio of the coloring composition shown in Table 5 (the ratio within the total amount of 43 parts of the coloring composition), photosensitive coloring Colored compositions [CR-2] to [CR-69] were obtained in the same manner as composition [CR-1]. Regarding the ratio change, the chromaticity of x=0.640 and y=0.330 was matched with the C light source when the coating film was evaluated.

<Evaluation of photosensitive coloring composition>
The luminance, contrast ratio and film thickness of the obtained photosensitive colored composition were measured by the following methods. Table 5 shows the evaluation results.

(Brightness evaluation)
The photosensitive coloring composition is applied onto a 100 mm × 100 mm glass substrate with a thickness of 1.1 mm using a spin coater, then dried at 70°C for 20 minutes, and an ultra-high pressure mercury lamp is used to apply an integrated amount of light of 150 mJ. /cm2 and developed with an alkaline developer at 23°C to obtain a coated substrate. After heating at 230° C. for 60 minutes and allowing to cool, the luminance Y(C) of the resulting coated substrate was measured using a microscopic spectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). After heat treatment at 230° C., the prepared coated substrate was made to match the chromaticity of x=0.640 and y=0.330 with a C light source. As an alkaline developer, from 1.5% by mass of sodium carbonate, 0.5% by mass of sodium bicarbonate, 8.0% by mass of anionic surfactant ("Perrex NBL" manufactured by Kao Corporation) and 90% by mass of water I used something. The brightness Y(C) was evaluated in four stages according to the following criteria.
◎: 20.5 or more (extremely good)
○: 20.0 or more and less than 20.5 (good)
△: 19.0 or more and less than 20.0 (defective)
×: less than 19.0 (extremely poor)

(Evaluation of contrast ratio)
Light emitted from the liquid crystal display backlight unit passes through the polarizing plate to be polarized, passes through the coating film of the coloring composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the planes of polarization of the polarizing plates are parallel to each other, the light is transmitted through the polarizing plates, but if the planes of polarization are perpendicular to each other, the light is blocked by the polarizing plates. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the coloring agent particles. When the polarizers are perpendicular to each other, some of the light is transmitted. This transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated as the contrast ratio.
[Contrast ratio] = [Brightness when parallel]/[Brightness when perpendicular]

Therefore, scattering caused by the colorants in the coating reduces the parallel brightness and increases the orthogonal brightness, thus lowering the contrast ratio. A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. Measurement was performed through a black mask with a 1 cm square hole in the measurement area. The same coating film that was used for the brightness evaluation was used. Evaluation was made on a scale of 4 according to the following criteria.
◎: 8000 or more (extremely good)
○: 7000 or more to less than 8000 (good)
△: 5000 or more to less than 7000 (defective)
×: less than 5000 (extremely poor)

(Evaluation of film thickness)
The film thickness was measured using the substrate on which the brightness was measured. A surface profilometer DEKTAK150 (manufactured by ULVAC ES, Inc.) was used to measure the film thickness. Evaluation was made on a scale of 4 according to the following criteria.
◎: film thickness less than 2.0 μm (extremely good)
○: film thickness 2.0 μm or more, less than 2.3 μm (practically good)
△: film thickness 2.3 μm or more, less than 3.0 μm (practical possible)
×: film thickness 3.0 μm or more (defective)

From Table 5, by using the coloring composition of the present invention, a photosensitive coloring composition that can be thinned with high brightness and a high contrast ratio when applied is obtained. In the case of using the coloring composition of the comparative example, in which the requirements of the manufacturing method of the present invention are partially or wholly excluded, any one of brightness, contrast ratio, and tinting strength is inferior.

<Manufacturing method of color filter>
A green photosensitive coloring composition and a blue photosensitive coloring composition for use in producing color filters were produced. For red, the photosensitive coloring composition [CR-22] of the present invention was used.

(Preparation of green colored composition [CP-71])
A mixture having the composition shown below was uniformly stirred and mixed, and after dispersing for 5 hours using zirconia beads with a diameter of 0.5 mm in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.), a particle size of 5.0 μm was obtained. to prepare a green colored composition [CP-71].
Green pigment (C.I. Pigment Green 36) 6.8 parts Yellow pigment (C.I. Pigment Yellow 150) 5.2 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 parts Acrylic resin Solution 1 35.0 parts PGMAc 52.0 parts

(Preparation of green photosensitive coloring composition [CR-70])
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition [CR-70].
Green coloring composition [CP-71] 42.0 parts acrylic resin solution [AR-2] 13.2 parts photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Aronix M402") 2.8 parts photoinitiator ( Ciba Japan "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts PGMAc 39.6 parts

(Preparation of blue colored composition [CP-72])
A mixture having the composition shown below was uniformly stirred and mixed, and after dispersing for 5 hours using zirconia beads with a diameter of 0.5 mm in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.), a particle size of 5.0 μm was obtained. to prepare a blue colored composition [CP-72].
Blue pigment (C.I. Pigment Blue 15:6) 7.2 parts Purple pigment (C.I. Pigment Violet 23) 4.8 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 parts Acrylic resin solution 1 35.0 parts PGMAc 52.0 parts

(Preparation of blue photosensitive coloring composition [CR-71])
A mixture having the following composition was uniformly stirred and mixed, and filtered through a 1 μm filter to prepare a blue photosensitive coloring composition [CR-71].
Blue colored composition [CP-72] 34.0 parts acrylic resin solution [AR-2] 15.2 parts photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Aronix M402") 3.3 parts photoinitiator ( Ciba Japan "Irgacure 907") 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts PGMAc 45.1 parts

A black matrix was patterned on a glass substrate, and the photosensitive coloring composition [CR-22] of the present invention was applied onto the substrate by a spin coater to form a colored film. The film was irradiated with ultraviolet rays of 300 mJ/cm 2 through a photomask using an extra-high pressure mercury lamp. Next, after removing unexposed portions by spray development with an alkali developer consisting of a 0.2% by weight sodium carbonate aqueous solution, the substrate is washed with deionized water, heated at 230° C. for 20 minutes, and red filter segments are formed. formed. The red filter segment formed was x=0.640, y=0.330 with C illuminant. By the same method, the green photosensitive coloring composition [CR-70] x = 0.300, y = 0.600, the blue photosensitive coloring composition [CR-71] x = 0.150, y = 0 A green filter segment and a blue filter segment were formed to obtain a color filter having a density of 0.060.

By using the photosensitive coloring composition (CR-22) of the present invention, it was possible to produce a high-brightness color filter.

Claims (8)

A pigment dispersant represented by the following general formula (1).
General formula (1):

[In general formula (1), R1 to R5 are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxy group, or the following general formula (2), general formula (3) or general formula ( 4) and n is 1 or 2; At least one of R1 to R5 is a group represented by general formula (2), general formula (3) or general formula (4). ]
General formula (2):

[In general formula (2), m is an integer of 1 to 10, and R6 and R7 each independently represent an alkyl group. ]
General formula (3):

[In general formula (3), R8 is a group represented by general formula (5). R9 is a chlorine atom, a hydroxy group, or a group represented by general formula (5) or chemical formula (6). ]
General formula (4):

[In general formula (4), R10 to R14 are a hydrogen atom, an alkoxy group, or a group represented by general formula (2) or general formula (3), and at least one of R10 to R14 is represented by general formula ( 2) or a group represented by the general formula (3). ]
General formula (5):

[In general formula (5), j is an integer of 1 to 10, and R15 and R16 each independently represent an alkyl group. ]
Chemical formula (6):

In general formula (1), R1 represents a hydrogen atom, an alkyl group or an alkoxy group, R2 and R5 are hydrogen atoms, one of R3 or R4 is a hydrogen atom, and the other is general formula (2) or general 2. The pigment dispersant according to claim 1, which is a group represented by formula (4). 3. The pigment dispersant according to claim 1, wherein n is 2. A pigment composition comprising the pigment dispersant according to any one of claims 1 to 3 and a pigment. The pigment is C.I. I. Pigment Red 176, Pigment Red 177, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 269, C.I. I. Pigment Red 291, a red pigment represented by general formula (7) and at least one selected from the group consisting of red pigment represented by general formula (8). thing.
General formula (7):

[In general formula (7), R17 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a trifluoromethyl group, and R18 to R22 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, Represents a trifluoromethyl group and -NHCONH- group. Adjacent groups of R18 to R22 may be linked by a -NHCONH- group to form a benzimidazolone ring. ]
General formula (8):

[In general formula (8), R represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a trifluoromethyl group, k is 1 or 2, and A is chemical formula (9), general formula (10) or It is a group represented by the general formula (11). ]
Chemical formula (9):

General formula (10):

[In general formula (10), R24 to R26 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group or an alkoxy group. ]
General formula (11):

[In general formula (11), B represents a direct bond or a divalent linking group. The divalent linking group includes an optionally substituted alkylene group, -O-, -S-, -CO-, -SO ₂ -, -COO-, -CONH-, and -SO ₂ NH-. show. ] A coloring composition comprising a coloring agent, a binder resin and an organic solvent, wherein the coloring agent contains the pigment composition according to claim 4 or 5. 7. The coloring composition according to claim 6, further comprising a photopolymerizable monomer. A color filter comprising a filter segment formed from the colored composition according to claim 7 on a substrate.