JP2012246393A - Pigment dispersant, pigment dispersion, colored resin composition for color filter, color filter, liquid crystal display device and organic light emitting display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersant capable of obtaining a colored layer with a high contrast and a high luminance, which has an excellent pigment dispersing property and dispersion stability without clouding hue even in the case of use in combination with an optional pigment, a pigment dispersion, and a colored resin composition for a color filter.SOLUTION: The pigment dispersant is made of a 1,3,5-triazine having at the 2,4,6 positions an arylamino group substituted by a sulfonic acid group and/or a sulfonamide group. Also provided are a pigment dispersion and a colored resin composition for a color filter, including the pigment dispersant.

Description

  The present invention relates to a pigment dispersant, a pigment dispersion, a colored resin composition for a color filter, a color filter, a liquid crystal display device, and an organic light emitting display device.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of home-use liquid crystal televisions is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, light passing through the color filter is directly colored into the colors of the pixels constituting the color filter, and the light of those colors is synthesized to form a color image. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.
Under such circumstances, demands for higher luminance, higher contrast, and improved color reproducibility are increasing in color filters. Recently, particularly for television applications, there is a growing demand for higher brightness due to reduced power consumption of the backlight and the characteristics of the LED backlight.

Here, the color filter is generally formed on a transparent substrate, a transparent layer formed on the transparent substrate, and composed of a colored layer of three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. And a light shielding portion formed.
As a method for forming such a colored layer, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.

  In general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  In order to realize a high contrast of the color filter, it has been studied to refine the pigment contained in the colored layer. As an attempt to refine the pigment, a pigment blend in which a pigment and a pigment derivative having a structure similar to the pigment are combined is used. However, although pigment derivatives have the effect of finely dispersing pigments with a specific structure, they cannot often be used for pigments with different structures. In addition, when there is absorption of a pigment derivative in the transmission wavelength region of the pigment, there is a problem that the color of the colored layer becomes cloudy and the luminance is lowered.

  Therefore, colorless or light-colored pigment dispersants have been developed as pigment dispersants that can be used for any pigment. For example, Patent Documents 1 to 3 disclose pigment dispersants having a triazine skeleton as colorless or light-colored pigment dispersants. However, the pigment dispersants disclosed in Patent Documents 1 and 2 tend to increase in viscosity over time, and the pigment dispersion stability is insufficient. Further, the pigment dispersant disclosed in Patent Document 3 is not focused on brightness and contrast, and the effect is unknown.

JP 2003-81972 A JP 2008-214515 A JP 2003-165922 A

The present invention has been made under such circumstances, and even when used in combination with an arbitrary pigment, the hue does not become turbid, the pigment has excellent dispersibility and dispersion stability, and has a high contrast and high brightness. The object is to provide a pigment dispersant from which
Furthermore, the present invention provides a pigment dispersion containing the pigment dispersant, a color resin composition for color filters containing the pigment dispersion, a color filter formed using the color resin composition for color filters, and An object of the present invention is to provide a liquid crystal display device and an organic light emitting display device having the color filter.

  The pigment dispersant according to the present invention is represented by the following general formula (1).

（一般式（１）中、Ｒ^１〜Ｒ^３は、それぞれ独立に、置換基を有していてもよい１〜３環のアリール基であって、同一であっても異なっていてもよい。Ｒ^４は、水素原子、炭素数１〜２０の直鎖若しくは分岐のアルキル基、カルボキシアルキル基又はスルホアルキル基であり、Ｒ^５は炭素数１〜２０の直鎖若しくは分岐のアルキル基、カルボキシアルキル基又はスルホアルキル基である。ｍはスルホ基の数を示し、ｎはスルホンアミド基の数を示し、前記Ｒ^１〜Ｒ^３の少なくとも１つに、少なくとも１つのスルホ基又はスルホンアミド基が結合する。ｍ及びｎは、それぞれ独立に、０以上の整数であって、ｍ＋ｎは１〜９の整数である。）

(In General Formula (1), R ^{1 to} R ³ are each independently a 1-3 ring aryl group which may have a substituent, and may be the same or different. R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a carboxyalkyl group or a sulfoalkyl group, and R ⁵ is a linear or branched alkyl group having 1 to 20 carbon atoms, carboxyalkyl. M represents the number of sulfo groups, n represents the number of sulfonamido groups, and at least one sulfo group or sulfonamido group is bonded to at least one of R ^{1 to} R ^3. M and n are each independently an integer of 0 or more, and m + n is an integer of 1 to 9.)

In the pigment dispersant according to the present invention, the substituent that R ^{1 to} R ³ may have is one or more selected from the group consisting of an alkyl group, an alkoxy group, a halogen atom, a carboxyl group, and a hydroxyl group. A substituent is preferred.

  The pigment dispersion according to the present invention contains a pigment, the pigment dispersant, a polymer dispersant, and a solvent.

  In the pigment dispersion according to the present invention, the polymer dispersant is preferably a basic polymer dispersant from the viewpoint of improving the dispersibility and dispersion stability of the pigment.

  The colored resin composition for a color filter according to the present invention contains the pigment dispersion and a curable binder component.

  The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers cures the colored resin composition for a color filter. It has the coloring layer formed in this way, It is characterized by the above-mentioned.

  The liquid crystal display device according to the present invention includes the color filter, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

  The organic light emitting display device according to the present invention includes the color filter and an organic light emitter.

  According to the present invention, there is provided a pigment dispersant that does not turbid hue even when used in combination with an arbitrary pigment, has excellent dispersibility and dispersion stability of the pigment, and provides a colored layer with high contrast and high brightness. Furthermore, a pigment dispersion containing the pigment dispersant, a colored resin composition for a color filter containing the pigment dispersion, a color filter formed using the colored resin composition for the color filter, and A liquid crystal display device and an organic light emitting display device having the color filter can be provided.

It is the schematic which shows an example of the color filter of this invention. It is the schematic which shows an example of the liquid crystal display device of this invention. It is the schematic which shows an example of the organic light emitting display apparatus of this invention.

Hereinafter, the pigment dispersant, the pigment dispersion, the color resin composition for color filter, the color filter, the liquid crystal display device and the organic light emitting display device of the present invention will be described in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either acrylate or methacrylate.
In addition, C.I. I. Pigment Red as “PR”, C.I. I. Pigment Blue may be abbreviated as “PB”.

1. Pigment dispersant The pigment dispersant of the present invention is represented by the following general formula (1).

（一般式（１）中、Ｒ^１〜Ｒ^３は、それぞれ独立に、置換基を有していてもよい１〜３環のアリール基であって、同一であっても異なっていてもよい。Ｒ^４は、水素原子、炭素数１〜２０の直鎖若しくは分岐のアルキル基、カルボキシアルキル基又はスルホアルキル基であり、Ｒ^５は炭素数１〜２０の直鎖若しくは分岐のアルキル基、カルボキシアルキル基又はスルホアルキル基である。ｍはスルホ基の数を示し、ｎはスルホンアミド基の数を示し、前記Ｒ^１〜Ｒ^３の少なくとも１つに、少なくとも１つのスルホ基又はスルホンアミド基が結合する。ｍ及びｎは、それぞれ独立に、０以上の整数であって、ｍ＋ｎは１〜９の整数である。）

(In General Formula (1), R ^{1 to} R ³ are each independently a 1-3 ring aryl group which may have a substituent, and may be the same or different. R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a carboxyalkyl group or a sulfoalkyl group, and R ⁵ is a linear or branched alkyl group having 1 to 20 carbon atoms, carboxyalkyl. M represents the number of sulfo groups, n represents the number of sulfonamido groups, and at least one sulfo group or sulfonamido group is bonded to at least one of R ^{1 to} R ^3. M and n are each independently an integer of 0 or more, and m + n is an integer of 1 to 9.)

  Furthermore, the pigment dispersant of this invention can also use a sulfo group and / or a sulfonamide group in the form of a salt depending on a use.

The inventors of the present invention have the structure represented by the above general formula (1), so that even when used in combination with any pigment, the present invention does not make the hue cloudy, and the dispersibility and dispersion stability of the pigment. It was found that a colored layer having excellent contrast and excellent contrast while maintaining high luminance can be obtained.
Since the pigment dispersant of the present invention is colorless or light and has a short absorption wavelength, even if a colored layer is formed in combination with pigments of any hue, the influence on the hue is extremely small and the color turbidity is small. In addition, a light-transmitting material with high luminance can be obtained. Moreover, since the pigment dispersant of this invention is excellent in the dispersibility and dispersion stability of a pigment, the colored layer excellent in contrast can be obtained.

In the said General formula (1), R < ¹ > -R < ³ > is the 1-3 ring aryl group which may have a substituent each independently, and it is preferable that it is especially 1 or 2 rings. If each aryl group of R ^{1 to} R ³ is 4 or more rings, the pigment dispersant may be colored, and the hue may be affected.
In the description of the group (atomic group) in the present invention, “may have a substituent” includes those having no substituent and those having a substituent.
Hereinafter, an aryl group which may have a substituent may be simply referred to as an “aryl group”.

  Examples of the 1-3 ring aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

The substituent that the aryl group may have is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, a halogen atom, a carboxyl group, a hydroxyl group, a heterocyclic group, and an ester group. Of these, an alkyl group, an alkoxy group, a halogen atom, a carboxyl group and a hydroxyl group are preferred. The aryl group can have one or more substituents selected from the group consisting of these substituents.
In view of dispersibility and dispersion stability, the aryl group preferably does not have a basic substituent.

The alkyl group is not particularly limited, but preferably has 1 to 20 carbon atoms. For example, the alkyl group may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, etc. It is done.
Although there is no restriction | limiting in particular as said alkoxy group, A C1-C20 alkoxy group is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, 2 -An ethylhexyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, a lauryloxy group, etc. are mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the pigment dispersant of the present invention, at least one sulfo group (—SO ₃ H) or sulfonamide group (—SO ₂ NR ⁴ R ⁵ ) is bonded to at least one of R ^{1 to} R ³ . In the general formula (1), m represents the number of sulfo groups, and n represents the number of sulfonamide groups. m and n are each independently an integer of 0 or more, and m + n is an integer of 1 to 9. Among these, from the viewpoint of steric hindrance and affinity with the dispersant, it is preferable that the aryl groups of R ^{1 to} R ³ have 3 or less sulfo groups and / or sulfonamido groups.

In the general formula (1), R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a carboxyalkyl group, or a sulfoalkyl group, and R ⁵ is a linear chain having 1 to 20 carbon atoms. Or it is a branched alkyl group, a carboxyalkyl group, or a sulfoalkyl group.
Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -Butyl group, t-pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group , Octadecyl group, nonadecyl group, icosyl group and the like. Especially, a C1-C10 thing is preferable and a C1-C3 thing is especially preferable.
The carboxyalkyl group is not particularly limited, and examples thereof include those having a carboxyl group (—COOH) at the terminal or side chain of the linear or branched alkyl group having 1 to 20 carbon atoms. Carboxyalkyl groups having a group are preferred.
The sulfoalkyl group is not particularly limited, and examples thereof include those having a sulfo group (—SO ₃ H) at the terminal or side chain of the linear or branched alkyl group having 1 to 20 carbon atoms. A sulfoalkyl group having a sulfo group is preferred.

The method for synthesizing the pigment dispersant according to the present invention is not particularly limited, and examples thereof include the following methods. First, in a solvent at 10 to 50 ° C., a primary aromatic amine having a sulfo group and / or a sulfonamide group and cyanuric chloride are reacted for 1 to 2 hours. Thereby, an aryl group having a sulfo group and / or a sulfonamido group is introduced into at least one of R ^{1 to} R ^{3 in} the general formula (1). Further, a primary aromatic amine having neither a sulfo group nor a sulfonamide group is added, and the temperature is raised to 30 to 100 ° C., followed by reaction for 1 to 5 hours. Thereby, in R ^{1 to} R ³ , an aryl group having neither a sulfo group nor a sulfonamide group is introduced at a position where an aryl group having a sulfo group or a sulfonamide group is not introduced. The obtained suspension is filtered, washed with an aqueous washing solution, and dried to obtain a pigment dispersant as a white product. The obtained pigment dispersant becomes colorless or pale when dissolved in a solvent.
In the above method, the number of the sulfo group and / or sulfonamide group that the primary aromatic amine has, and the molar ratio of cyanuric chloride to the primary aromatic amine having the sulfo group and / or the sulfonamide group, By adjusting the reaction solution concentration, reaction temperature, reaction time, etc., the amount of sulfo group and sulfonamide group introduced per molecule of the resulting compound can be controlled.
In addition, salts, such as a metal salt of the compound represented by the said General formula (1), ammonium salt, an amine salt, can be obtained by a conventionally well-known method.

  In addition, as a method for synthesizing the pigment dispersant according to the present invention, it is sufficient that the product contains the pigment dispersant of the present invention represented by the above general formula (1). A small amount of a compound not containing an amide group, that is, a compound represented by m + n = 0 in the general formula (1) may be contained.

2. Pigment Dispersion The pigment dispersion according to the present invention is characterized by containing a pigment, the pigment dispersant described above, a polymer dispersant, and a solvent.

Since the pigment dispersion according to the present invention is dispersed by the pigment dispersant represented by the general formula (1), even if any pigment is used, the pigment is excellent in dispersibility and dispersion stability. The colored layer obtained using the pigment dispersion according to the invention is excellent in contrast and brightness.
The pigment dispersion according to the present invention contains a pigment, a pigment dispersant represented by the general formula (1) according to the present invention, a polymer dispersant, and a solvent as essential components. And may contain other components.
Hereinafter, each component of the pigment dispersion according to the present invention will be described in detail.

(Pigment)
The pigment contained in the pigment dispersion according to the present invention is not particularly limited, and various organic or inorganic pigments can be used. Specific examples of organic pigments include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (C.I. ) Can be listed. C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Yellow pigments such as C.I. Pigment Yellow 185; I. Pigment orange 38, C.I. I. Pigment orange 71, C.I. I. Orange pigments such as CI Pigment Orange 73; I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Red pigments such as CI Pigment Red 272; and C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. Blue pigments such as CI Pigment Blue 15: 6; I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Green pigments such as C.I. Pigment Green 58; I. Pigment violet 19, C.I. I. Pigment violet 23 and the like. Further, phthalocyanine having a high bromination rate, which has been difficult to disperse in the past, such as high brightness G pigments such as Monastral Green 6YC and 9YC (manufactured by Avisia Co., Ltd.), metals other than Cu and Zn as the central metal, for example, High color purity G pigments made of different metal phthalocyanine pigments such as Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Ge, and Sn can be used.

  Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and oxidation. Examples thereof include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In this invention, a pigment can be used individually or in mixture of 2 or more types.

  Among these pigments, the pigment dispersion according to the present invention can impart excellent dispersibility to various pigments widely used in color filters for liquid crystal display devices. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15: 6 and C.I. I. It can be suitably used when preparing a pigment dispersion containing at least one selected from the group consisting of CI Pigment Violet 23, the phthalocyanine pigment having a high bromination rate, and the different metal phthalocyanine pigment.

(Pigment dispersant)
The pigment dispersion according to the present invention contains a pigment dispersant represented by the general formula (1). As the pigment dispersant, the same ones as described above can be used, and the description thereof is omitted here.
In the pigment dispersion of the present invention, the content of the pigment dispersant represented by the general formula (1) is not particularly limited as long as it is appropriately adjusted. Usually, the content of the pigment dispersant represented by the general formula (1) is preferably in the range of 0.5 to 25 parts by weight, more preferably 1.0 to 20 with respect to 100 parts by weight of the pigment. It is preferably within the range of parts by weight.
In addition, when a pigment derivative is contained in the pigment dispersion liquid, the pigment used to define the content includes a pigment derivative in addition to the pigment.

(Polymer dispersant)
Furthermore, the pigment dispersion of the present invention contains a polymer dispersant. By using a combination of the pigment dispersant represented by the general formula (1) and the polymer dispersant, the pigment dispersion of the present invention is excellent in pigment dispersibility and dispersion stability, and has high contrast and brightness. A layer can be formed.

  Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; amides obtained by the reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyester, salts thereof, and the like.

Among these, as the polymer dispersant used in the pigment dispersion of the present invention, a basic polymer dispersant is preferable. This is because when used in combination with the pigment dispersant represented by the general formula (1), the pigment dispersion has a higher pigment dispersibility and dispersion stability effect.
Further, a block copolymer type or graft copolymer (comb type) type polymer dispersant in which a pigment adsorption site and a solvent affinity site are functionally separated in the molecule is preferable, and a tertiary amine salt or quaternary is particularly preferable. A block copolymer containing an ammonium salt is preferred. In such a block copolymer, a block portion containing a tertiary amine salt or a quaternary ammonium salt is adsorbed to the pigment and the pigment dispersant represented by the general formula (1), and the tertiary amine salt is absorbed. Or since the block part which does not contain a quaternary ammonium salt has solubility with respect to a solvent, the dispersibility of a pigment can be improved. In particular, in the present invention, when a pigment dispersant represented by the above general formula (1) and a polymer dispersant composed of a salt-type block copolymer are used in combination, it is possible to realize particularly finer pigments. Thus, the contrast can be improved. By using a polymer dispersant made of a block copolymer, the size of the pigment adsorbing part and the solvent-soluble part can be designed smaller than when using a graft polymer type polymer dispersing agent. Increases effectiveness.

Examples of the tertiary amine salt include a salt formed at a tertiary amine moiety such as dimethylaminoethyl acrylate, which is a unit forming a block copolymer, with an acid such as a phosphoric acid compound or a sulfonic acid compound. In addition, examples of the quaternary ammonium salt include a quaternary ammonium salt such as dimethylaminoethyl acrylate, which is a unit that forms a block copolymer, at a tertiary amine moiety by an allyl halide and / or an aralkyl halide. It is done.
The block portion containing a tertiary amine salt or a quaternary ammonium salt may contain an amine that does not form a salt.

  The amount of the tertiary amine salt or quaternary ammonium salt contained in the copolymer is preferably 1 to 50% in terms of the number of repeating units relative to the total number of repeating units of the block copolymer, in particular. It is preferable that it is 1 to 20%.

  Examples of the main chain structure of the polymer include (meth) acrylic resins and styrene resins. Among these, a (meth) acrylic resin is preferable in that it easily synthesizes a block copolymer.

  The weight average molecular weight Mw of the block copolymer containing a tertiary amine salt or a quaternary ammonium salt used in the present invention is preferably in the range of 500 to 20000, and preferably in the range of 1000 to 15000. More preferably, it is still more preferably in the range of 3000-12000. By being within the above range, it becomes possible to achieve both wettability and dispersion stability with respect to a pigment in the initial stage of dispersion in which the pigment is uniformly dispersed. Here, the weight average molecular weight can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).

  The polymer dispersant used in the present invention includes, among others, a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II). Furthermore, it is a block copolymer in which at least a part of the amino group of the repeating unit (1) and an organic acid compound and / or a halogenated hydrocarbon form a salt, particularly a coating film with improved contrast. This is preferable because it can be manufactured.

［式（Ｉ）及び式（ＩＩ）中、Ｒⁱは、水素原子又はメチル基、Ｒⁱⁱ及びＲⁱⁱⁱは、それぞれ独立に水素原子又は炭素数１〜８のアルキル基、Ａは、炭素数１〜８のアルキレン基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−（ＣＨ_２）_ｙ−で示される２価の基、Ｒ^ivは、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−[ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ]_ｘ−Ｒ^８又は−[（ＣＨ_２）_ｙ−Ｏ]_ｚ−Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素数が１〜５のアルキル基である。上記アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ置換基を有していても良い。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。ｋは３〜２００の整数、ｌは１０〜２００の整数を示す。］

[In Formula (I) and Formula (II), R ⁱ is a hydrogen atom or a methyl group, R ⁱⁱ and R ⁱⁱⁱ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( R 2 is a divalent group represented by CH ₂ ) _y —, R ^iv is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH It is a monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, It is a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. k represents an integer of 3 to 200, and l represents an integer of 10 to 200. ]

<Block copolymer>
The block copolymer has a repeating unit (1) represented by the general formula (I) and a repeating unit (2) represented by the general formula (II). In the general formula (I), R ⁱ represents a hydrogen atom or a methyl group, and R ⁱⁱ and R ⁱⁱⁱ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable. In the present invention, R ⁱⁱ and R ⁱⁱⁱ may be the same as or different from each other.

A is an alkylene group having 1 to 8 carbon atoms, * — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — **, or * — _{[(CH 2) y -O]} z - (CH 2) y - is a divalent group represented by **. Here, * represents a linking site on the ester bond side, and ** represents a linking site on the amino group side. The alkylene group having 1 to 8 carbon atoms may be linear or branched. For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various kinds. Hexylene group and various octylene groups.
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2. In the present invention, if x, y, and z are within the above ranges, the pigment dispersion of the present invention has excellent pigment dispersibility.
As said A, a C1-C8 alkylene group is preferable and a methylene group and ethylene group are more preferable. If the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be kept good.

In the general formula (II), R ^iv represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (R ⁷ ) —. O] _x -R ⁸ or - indicates a _{[(CH 2) y -O]} z -R 8.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , Sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups, cyclohexane Examples include an octyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, propenyl groups, various butenyl groups, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecenyl groups, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that there is a double bond at the terminal of the alkenyl group.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred carbon number does not include the carbon number of the substituent.

R ⁶ and R ⁷ are the same as described above, and R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aralkyl group. , An aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , wherein R ⁹ is a hydrogen atom or a linear, branched, or cyclic group having 1 to 5 carbon atoms. It is an alkyl group.
In the monovalent group represented by R ⁸ , the substituent that may be included is, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a halogen atom such as F, Cl, or Br. And so on.
The alkyl group having 1 to 18 carbon atoms of R ^8, and alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the R ^iv.
In the above R ^iv , x, y and z are as described in A above.
In addition, R ^iv in the repeating unit (2) represented by the general formula (II) may be the same as or different from each other.

In the present invention, as R ^iv , it is preferable to use one having excellent solubility with a solvent described later, and specifically, it varies depending on the repeating unit constituting the block copolymer. When the solvent is an ether alcohol acetate solvent, an ether solvent, an ester solvent or the like generally used as a solvent for a color filter, a methyl group, an ethyl group, an n-butyl group, 2- An ethylhexyl group, a benzyl group and the like are preferable. Moreover, when the said solvent is a thing with lower polarity, such as pentane and hexane, it is preferable to use a pentyl group, a hexyl group, a heptyl group, etc.
Here, the reason for setting R ^iv in this way is that the repeating unit (2) containing R ^iv has high solubility in the solvent, and the amino group of the repeating unit (1), This is because the dispersibility and stability of the pigment can be made particularly excellent when the salt-forming site formed by the organic acid compound described later has a high adsorptivity to the pigment.

Further, R ^iv is substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group as long as it does not interfere with the dispersion performance of the block copolymer. Alternatively, after the synthesis of the block copolymer, the substituent may be added by reacting with the compound having the substituent. Moreover, after synthesizing a block copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting a block copolymer having a carboxyl group with glycidyl (meth) acrylate, or reacting a block copolymer having an isocyanate group with hydroxyethyl (meth) acrylate. Can do.

  The ratio k / l of the number k of units of the structural unit (1) and the number of units 1 of the structural unit (2) of the block copolymer used in the present invention is preferably in the range of 0.01 to 1. More preferably, it is in the range of 0.05 to 0.5. When the ratio k / l is within the above range, the adsorptivity to the pigment is good, the solubility of the structural unit (2) in the solvent is not lowered, and the dispersibility and stability of the pigment are lowered. There is nothing to do.

Regarding the molecular size of the block copolymer used in the present invention, the number k of the repeating units (1) is an integer of 3 to 200, preferably an integer of 3 to 50. The number l of the repeating unit (2) is an integer of 10 to 200, preferably an integer of 20 to 100, more preferably an integer of 20 to 70. In the present invention, when k and l are within the above ranges, the solvent-soluble part and the solvent-insoluble part act effectively, and the pigment dispersion of the present invention is excellent in pigment dispersibility. can do.
Further, the weight average molecular weight Mw of the block copolymer is preferably in the range of 500 to 20000, more preferably in the range of 1000 to 15000, and further preferably in the range of 3000 to 12000. preferable. By being within the above range, it becomes possible to achieve both wettability and dispersion stability with respect to a pigment in the initial stage of dispersion in which the pigment is uniformly dispersed.

  The weight average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.).

  The binding order of the block copolymer used in the present invention is not particularly limited as long as it has the repeating unit (1) and the repeating unit (2) and can stably disperse the pigment. However, it is preferable that the repeating unit (1) is bonded to only one end of the block copolymer. That is, the repeating unit (1) and the repeating unit (2) may be bonded in the order of repeating unit (1) -repeating unit (2), or repeating unit (1) -repeating unit. (2) -repeated unit (1) may be bonded in this order, or repeating unit (1) -repeating unit (2) may be bonded repeatedly, but in the present invention, However, those bonded in the order of repeating unit (1) -repeating unit (2) are preferred. The reason is that it is excellent in the adsorptivity with respect to a pigment, and also the aggregation of polymer dispersants using such a block copolymer can be effectively suppressed.

  In the case where two or more structural units (1) and structural units (2) are included, a block copolymer in which the structural units (1), the structural units (2 ′), and the structural units (2 ″) are combined in this order, A block copolymer bonded in the order of structural unit (1 ')-structural unit (1 ")-structural unit (2), or structural unit (1')-structural unit (1")-structural unit (2 ') -The block copolymer etc. which couple | bonded in order of the structural unit (2 ") may be sufficient.

<Organic acid compound>
An amino group contained in the structural unit (1) of the block copolymer having the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II); Examples of the organic acid compound that forms a salt include an organic phosphoric acid compound having a structure represented by the following general formula (III) and / or an organic sulfonic acid compound having a structure represented by the following general formula (IV). It is done.

［式（ＩＩＩ）及び式（ＩＶ）中、Ｒ^ａ及びＲ^ａ’はそれぞれ独立に、水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅ、又は−Ｏ−Ｒ^ａ’’で示される１価の基であり、Ｒ^ａ及びＲ^ａ’のいずれかは炭素原子を含む。Ｒ^ａ’’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅで示される１価の基である。
Ｒ^ｂは、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅ、又は−Ｏ−Ｒ^ｂ’で示される１価の基である。Ｒ^ｂ’は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^ｃ）−ＣＨ（Ｒ^ｄ）−Ｏ］_ｓ−Ｒ^ｅ、又は−［（ＣＨ_２）_ｔ−Ｏ］_ｕ−Ｒ^ｅで示される１価の基である。
Ｒ^ｃ及びＲ^ｄは、それぞれ独立に水素原子又はメチル基であり、Ｒ^ｅは、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^ｆで示される１価の基であり、Ｒ^ｆは水素原子又は炭素数１〜５のアルキル基である。Ｒ^ａ、Ｒ^ａ’、及びＲ^ｂにおいて、アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ、置換基を有していてもよい。
ｓは１〜１８の整数、ｔは１〜５の整数、ｕは１〜１８の整数を示す。］

[In Formula (III) and Formula (IV), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. 1 represented by the group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″.} the valence of the group, one of R ^a and R ^{a 'comprises} a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{b ′} . R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or _- it is a monovalent group represented by _{[(CH 2) t -O]} u -R e.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, _{-CHO, -CH 2 CHO, -CO-} CH = CH 2, a monovalent group represented by _{-CO-C (CH 3) =} CH 2 or _-CH 2 COOR ^{f, R f} is hydrogen or C It is an alkyl group of formula 1-5. In R ^a , R ^{a ′} , and R ^b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. ]

  In the present invention, by using the organic acid compound and / or a halogenated hydrocarbon described later, the polymer dispersant can be excellent in dispersibility and stability of the pigment. Furthermore, when an organic acid compound is used, the salt-forming site has high solubility in an aqueous alkali solution at the time of alkali development, so that it can be excellent in alkali developability. In particular, as the particle diameter of pigments for improving contrast becomes smaller, a large amount of polymer dispersant is required, which may cause problems such as deterioration in alkali developability and increase in residues. Such problems can be reduced when an organic acid compound is used in the dispersant.

In the general formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, or — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} , R ^a and R ^a Any of ^' includes carbon atoms.

The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aryl group, and the aralkyl group are as described above for R ^iv . The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that the alkenyl group has a double bond at the terminal.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, nitro groups, and the like.
In addition, examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include alkenyl groups, nitro groups, and halogen atoms in addition to linear or branched alkyl groups having 1 to 4 carbon atoms. .

R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^f , and R ^f is a hydrogen atom or It is a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.

In the monovalent group represented by R ^e, Examples of the substituent which may have, for example, linear 1 to 4 carbon atoms, branched or cyclic alkyl group, F, Cl, halogen atom such as Br And so on.
The alkyl group having 1 to 18 carbon atoms in the R ^e is as shown in the above R ⁴ , and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms are the same as the above R ^a and R ^{a ′.} It is as shown in.

When R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R. ^e is a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the above ^{R a} and R ^{a '.} In addition, when R ^{a ″} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.

In R ^a , R ^{a ′} and R ^{a ″} , s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. s is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

In the general formula (IV), R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —. _O] s ^-R _e, - shows a _{[(CH 2) t -O]} u -R e, or -O-R ^{b '.}
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group is as shown by the above ^{R a} and R ^{a '.}

When R ^b is —O—R ^{b ′} , it is an acidic sulfate ester. R ^{b ′} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. ,-[(CH ₂ ) _t —O] _u —R ^e .
In R ^b and R ^{b ′} , each of the alkyl group, alkenyl group, aralkyl group and aryl group may have a substituent.
The alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl ^{group, - [CH (R c)} -CH (R d) -O] s -R e, - [(CH ₂ ) _t— O] _u —R ^e is as described above for R ^a , R ^a and R ^{a ″} .
R ^c , R ^d, and R ^e are as described above for R ^a , R ^a, and R ^{a ″} .
In said ^Rb and ^{Rb '} , s is an integer of 1-18, t is an integer of 1-5, u is an integer of 1-18. Preferred s, t, and u are the same as R ^a , R ^{a ′} and R ^{a ″} described above.

As the organic acid compound represented by the general formula (III), R ^a and R ^{a ′} in the general formula (III) each independently have a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or a substituent. Aryl group or aralkyl group, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e or a monovalent group represented by —O—R ^{a ″} , one of R ^a and R ^{a ′} contains a carbon atom, and R ^{a ″} is a methyl group, ethyl Group, aryl group or aralkyl group which may have a substituent, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) and _{^{t -O] u -R e, R}} c and ^{R d} are each independently a hydrogen atom or a methyl group Ri, from the viewpoint of can be made of those ^{R e} is -CO-CH = CH ₂ or _{-CO-C (CH} 3) a = CH ₂ is excellent in pigment dispersibility.

Moreover, as an organic acid compound represented by general formula (IV), ^Rb in general formula (IV) is a methyl group, an ethyl group, the aryl group which may have a substituent, an aralkyl group, a vinyl group. , An allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{b ′} R ^{b ′} is a methyl group, an ethyl group, an aryl group or an aralkyl group optionally having a substituent, a vinyl group, an allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) t—O] _u —R ^e , wherein R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e also There what is -CO-CH = CH ₂ or _{-CO-C (CH 3) =} CH 2 is excellent in pigment dispersibility From the viewpoint which can be.

Of these, organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' From the viewpoint of pigment dispersibility, it preferably has an aromatic ring. At least one of R ^a , R ^{a ′} and R ^{a ″} , or R ^b or R ^{b ′} , an aryl group or aralkyl group which may have a substituent, more specifically, a benzyl group, A phenyl group, a tolyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of pigment dispersibility. In the general formula (III), when one of R ^a and R ^{a ′} has an aromatic ring, the other of R ^a and R ^{a ′} is preferably a hydrogen atom or a hydroxyl group.

Further, from the viewpoint of heat resistance and chemical resistance, particularly alkali resistance, the organic acid compounds represented by the general formula (III) and the general formula (IV) include carbon (P) and sulfur (S). A compound in which atoms are directly bonded is preferable, and R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl A monovalent group represented by a group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , R ^a and Any of R ^{a ′} preferably contains a carbon atom. R ^b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e. , — [(CH ₂ ) _t —O] _u —R ^e is preferably a monovalent group.

The organic acid compound represented by the general formula (III) and general formula ^{(IV), R} a, R ^{a 'and} / or R ^a'', and / or as ^{R b} and / or R ^b' Has a polymerizable group, that is, a vinyl group, an allyl group, or — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u. It is preferable that -R ^e and R ^e is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , especially R ^a , R ^{a ′} and / or R ^{a ′. '} And / or R ^b and / or R ^b' are preferably vinyl, allyl, 2-methacryloyloxyethyl, or 2-acryloyloxyethyl.
In such a case, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups and the color filter of the present invention are exposed during exposure when forming a colored layer using the colored resin composition for a color filter of the present invention. The alkali-soluble resin and the polyfunctional monomer contained in the colored resin composition can be easily polymerized, and the polymer dispersant can be stably present in the colored layer of the color filter. . When a liquid crystal display device is manufactured using such a color filter, the polymer dispersant can be prevented from bleeding out to the liquid crystal layer or the like.

  In addition, since the organic acid compound contains a polymerizable group, the polymerizable group of the organic acid compound can be polymerized before being used for forming the colored layer, and as a result, the polymer dispersant has a high molecular weight. Therefore, the colored resin composition for a color filter at an unexposed portion can be made particularly excellent in alkali developability during development for forming a colored layer.

  In addition, the organic acid compound represented by the said general formula (III) and general formula (IV) can be used individually by 1 type or in combination of 2 or more types.

<Halogenated hydrocarbon>
The halogenated hydrocarbon used in the present invention is a block copolymer having the above-mentioned repeating unit (1) represented by the general formula (I) and the repeating unit (2) represented by the general formula (II). A salt is formed with the amino group of the repeating unit (1).
In the present invention, by using the above-mentioned halogenated hydrocarbon, the salt-forming site produced by the polymer dispersant is excellent in adsorptivity to the pigment, so that high dispersibility can be expressed and at the same time The heat resistance and alkali resistance of the molecular dispersant can be increased.

Examples of the halogenated hydrocarbon include those in which any one of a chlorine atom, a bromine atom and an iodine atom is substituted with a hydrogen atom of a saturated or unsaturated linear, branched or cyclic hydrocarbon. . Among these, a halogenated hydrocarbon in which one of the hydrogen atoms of the hydrocarbon is substituted with a halogen atom is preferable from the viewpoint of forming a salt with the polymer dispersant and improving the pigment dispersibility.
The halogenated hydrocarbon may be linear, branched or cyclic. The number of carbon atoms is preferably 1-18, and more preferably 1-7.

  Among the halogenated hydrocarbons, examples of the halogenated alkyl include those having 1 to 18 carbon atoms, but are not particularly limited. Specifically, for example, methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, etc. Can be mentioned. Examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. Further, examples of the aralkyl group of the halogenated aralkyl include those having 7 to 18 carbon atoms, but are not particularly limited. Specific examples include benzyl chloride, benzyl bromide, benzyl iodide, naphthylmethyl chloride, pyridylmethyl chloride, naphthylmethyl bromide, pyridylmethyl bromide and the like.

  Among these, at least one selected from the group consisting of benzyl halide, allyl halide, and methyl halide is easy to form a salt, and the formed salt-forming site has excellent adsorptivity to the pigment. This is preferable.

  The content of the organic acid compound and / or halogenated hydrocarbon in the block copolymer used in the present invention is not particularly limited as long as good dispersion stability is exhibited. It is about 0.01-2.0 molar equivalent with respect to the tertiary amino group represented by (I), More preferably, it is 0.1-1.0 molar equivalent. In such a case, the pigment dispersibility and the pigment dispersion stability are excellent. In addition, when using 2 or more types of the said organic acid compound and / or halogenated hydrocarbon together, content which added these should just be in the said range.

<Manufacture of polymer dispersant made of salt type block copolymer>
In the present invention, as a method for producing a block copolymer used as a polymer dispersant, an amino group having the repeating unit (1) and the repeating unit (2) and having the repeating unit (1) is used. And the above-mentioned organic acid compound and / or halogenated hydrocarbon may be any method that can produce a salt, and is not particularly limited. In the present invention, for example, the repeating unit (1) and the repeating unit (2) are polymerized using a known polymerization means, and then dissolved or dispersed in a solvent described later, and then the organic acid is dissolved in the solvent. A block copolymer can be produced by adding a compound and / or a halogenated hydrocarbon and stirring.

  The polymerization means is not particularly limited as long as it is a means capable of polymerizing the above repeating unit (1) and repeating unit (2) in a desired number to obtain a desired molecular weight, and has a vinyl group. A method generally used for polymerization of a compound can be employed, and for example, anionic polymerization, living radical polymerization, or the like can be used. In the present invention, among them, a method in which polymerization proceeds in a living manner, such as group transfer polymerization (GTP) disclosed in “J. Am. Chem. Soc.” 105, 5706 (1983), is used. preferable. According to this method, it is easy to make the molecular weight, molecular weight distribution, etc. within a desired range, so that the dispersibility of the polymer dispersant can be made uniform.

  Further, in the pigment dispersion of the present invention, the content of the polymer dispersant used suitably in combination with the pigment dispersant represented by the general formula (1) is not particularly limited as long as it is appropriately adjusted. Usually, the content of the polymer dispersant is preferably in the range of 10 to 150 parts by weight, particularly preferably in the range of 15 to 40 parts by weight with respect to 100 parts by weight of the pigment. In addition, when a pigment derivative is contained in the pigment dispersion liquid, the pigment used to define the content includes a pigment derivative in addition to the pigment.

(solvent)
The pigment dispersion according to the present invention contains a solvent for dispersing the pigment. The solvent used in the pigment dispersion is not particularly limited as long as it is an organic solvent that does not react with each component in the pigment dispersion and can dissolve or disperse them.
Examples of the solvent that can be used in the pigment dispersion of the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; Carbitol solvents such as ethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; Methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate Cellosolve acetate solvents such as ethoxyethyl acetate and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Ether solvents such as propylene glycol monomethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; benzene and toluene , Xylene, naphthalene and other unsaturated hydrocarbon solvents; N-heptane, N-hexane, N-octane, etc. Organic solvents, such as a saturated hydrocarbon solvent, are mentioned. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; methyl methoxypropionate, ethoxypropionic acid Ester solvents such as ethyl and ethyl lactate; ketone solvents such as cyclohexanone are preferred Used. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl- One or more selected from the group consisting of 1-butyl acetate, 3-methoxybutyl acetate and cyclohexanone is preferable from the viewpoint of solubility of other components and coating suitability.

These solvents may be used alone or in combination of two or more.
The pigment dispersion of the present invention is prepared by using the above solvent in a proportion of usually 60 to 85% by weight with respect to the total amount of the pigment dispersion containing the solvent. When the amount of the solvent is too small, the viscosity increases and the pigment dispersibility tends to decrease. Moreover, when there are too many solvents, a pigment density | concentration will fall and it may be difficult to achieve the chromaticity coordinate which makes a resin composition the target after preparation.

(Other ingredients)
The pigment dispersion of the present invention may further contain other components such as a pigment dispersant other than the pigment dispersant and polymer dispersant represented by the general formula (1), and a pigment dispersion auxiliary resin, as necessary. You may mix.

  Examples of the pigment dispersant other than the pigment dispersant and the polymer dispersant represented by the general formula (1) include pigment derivatives that are compatible with the pigment to be used. The pigment derivative is a compound having a role of imparting a functional group to the pigment skeleton and adding various functions to the pigment. When a pigment derivative is added to the pigment at the time of pigment dispersion, the pigment-like skeleton of the pigment derivative is adsorbed or bonded to the surface of the pigment, whereby the surface of the pigment becomes polar, so that the affinity between the dispersant and the pigment is increased. It is considered that the dispersibility and dispersion stability can be secured. In addition, a known pigment dispersant can be appropriately used in the pigment dispersion of the present invention as necessary.

  Examples of the pigment dispersion auxiliary resin include alkali-soluble resins exemplified by a resin composition described later. In some cases, the steric hindrance of the alkali-soluble resin makes it difficult for the pigment particles to come into contact with each other, and may have the effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.

  Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

<Method for producing pigment dispersion>
The pigment dispersion of the present invention preferably has a step of dispersing the pigment in the solvent in the presence of the pigment dispersant represented by the general formula (1) and the polymer dispersant.
In the dispersion process, as a disperser for performing dispersion treatment, a roll mill such as a two-roll or a three-roll, a ball mill such as a ball mill or a vibration ball mill, a paint conditioner, a continuous disk type bead mill, a bead mill such as a continuous annular type bead mill, or the like. Can be mentioned. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.05 to 1.0 mm.

  In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited. For example, when a paint shaker is used so that the average dispersion particle size of the pigment is about 15 to 70 nm. Is preferably 5 to 50 hours from the viewpoint of realizing high contrast by refining the pigment.

  In this way, a pigment dispersion having excellent pigment particle dispersibility is obtained. The pigment dispersion is used as a preliminary preparation for preparing a colored resin composition for a color filter having excellent pigment dispersibility.

  As the pigment dispersibility of the pigment dispersion thus obtained, the viscosity at 23 ° C. is preferably 10.0 mPa · s or less, and more preferably 8.0 mPa · s or less. As dispersion stability, the viscosity when left at 23 ° C. for 1 week is also preferably 10.0 mPa · s or less, more preferably 8.0 mPa · s or less. Here, the viscosity at 23 ° C. can be determined by measuring the viscosity at 6 rpm using a rheometer (for example, rheometer MCR-301 manufactured by Anton Paar (cone plate CP50-1)).

3. Colored resin composition for color filter The colored resin composition for a color filter according to the present invention contains the pigment dispersion according to the present invention and a curable binder component.
According to the colored resin composition for a color filter according to the present invention, by including the pigment dispersion according to the present invention, the colored layer is excellent in the dispersibility and dispersion stability of the pigment and excellent in contrast while maintaining high luminance. Is obtained.
Hereinafter, the components used in the colored resin composition for a color filter of the present invention will be described.
The components that can be contained in the pigment dispersion according to the present invention can be the same as those described in the section of the pigment dispersion, and thus the description thereof is omitted here.

(Curable binder component)
The colored resin composition for a color filter according to the present invention contains a curable binder component in order to impart film formability and adhesion to a surface to be coated, and to impart sufficient hardness to the coating film. It does not specifically limit as a curable binder component, The curable binder component used in forming the coloring layer of a conventionally well-known color filter can be used suitably.
Examples of the curable binder component include a curable binder component including a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. What contains a thermosetting binder component can be used.

When the colored resin composition for a color filter according to the present invention can be selectively adhered in a pattern on a substrate to form a colored layer, for example, when used in an inkjet method, the developability of the curable binder component Is not necessary. In this case, a well-known thermosetting binder component, a photocurable binder component, etc. which are used when forming a color filter coloring layer by an inkjet system etc. can be used suitably.
On the other hand, when using a photolithography system when forming a colored layer, the photosensitive binder component which has alkali developability is used suitably.
Hereinafter, the photosensitive binder component and the thermosetting binder component suitable for use in the ink jet system will be described in detail, but the curable binder component is not limited thereto.

(1) Photosensitive binder component Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include an alkali-soluble resin and a system containing an o-quinonediazide group-containing compound as a photosensitizing component, and examples of the alkali-soluble resin include a polyimide precursor.

  As the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator is suitably used. Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photopolymerization initiator will be specifically described.

<Alkali-soluble resin>
The alkali-soluble resin has a carboxyl group in the side chain, acts as a binder resin, and is appropriately selected and used as long as it is soluble in a developer used for pattern formation, particularly preferably in an alkali developer. be able to.
A preferable alkali-soluble resin in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the photosensitive resin composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the photosensitive resin composition, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Examples of the acrylic copolymer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, styrene, and 2-hydroxylmethyl (meth) acrylate. Examples thereof include a copolymer comprising one or more selected from among them and one or more selected from anhydrides such as (meth) acrylic acid, maleic acid, fumaric acid, and vinyl acetic acid. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by weight, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by weight, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

  The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group is not particularly limited, but is preferably 1000 to 40000, more preferably 2000 to 5000.

  One kind of alkali-soluble resin may be used, or two or more kinds may be used in combination. The content thereof is usually 100 parts by weight of the pigment contained in the colored resin composition for color filters. It is in the range of 10 to 1000 parts by weight, preferably in the range of 20 to 500 parts by weight. If the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is too large, the ratio of the pigment becomes relatively low and sufficient coloring is achieved. The concentration may not be obtained.

<Multifunctional monomer>
The polyfunctional monomer used in the colored resin composition for a color filter of the present invention is not particularly limited as long as it can be polymerized by a photopolymerization initiator described later, and usually contains an ethylenically unsaturated double bond. A compound having two or more compounds is used, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.

A polyfunctional (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the color resin composition for a color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. The poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid-modified products are preferred. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Succinic acid modification of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) Dipentae modified acrylate succinate Sri Tall hexa (meth) acrylate are preferable.
Although there is no restriction | limiting in particular in content of the said polyfunctional monomer, Usually, about 5-500 weight part with respect to 100 weight part of said alkali-soluble resin, Preferably it is the range of 20-300 weight part. If the content of the polyfunctional monomer is less than the above range, the photocuring may not proceed sufficiently, and the exposed part may be eluted. There is a risk.

<Photopolymerization initiator>
There is no restriction | limiting in particular as a photoinitiator used in the colored resin composition for color filters of this invention, It can select suitably from various photoinitiators known conventionally. For example, aromatic ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone, 2-ethylanthraquinone and phenanthrene, benzoin ethers such as benzoin methyl ether and benzoin phenyl ether, benzoins such as methyl benzoin and ethyl benzoin, 2- (o -Chlorophenyl) -4,5-phenylimidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4 Halomethyloxadiazole compounds such as oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S -Triazine, 2- (4-butoxy- Halomethyl-S-triazine compounds such as naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, Benzyl, benzoylbenzoic acid, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, α-dimethoxy- Examples include α-phenylacetophenone and phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  Content of a photoinitiator is about 0.01-100 weight part normally with respect to 100 weight part of said polyfunctional monomers, Preferably it is 5-60 weight part. If this content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the hardness of the colored layer may not be sufficient. There may be a case where the content of the pigment or the like in the solid content of the composition is relatively reduced, and a sufficient coloring density cannot be obtained.

(2) Thermosetting binder component As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of promoting a thermosetting reaction is used. It may be added. Examples of the thermosetting functional group include an epoxy group, an oxetanyl group, an isocyanate group, and an ethylenically unsaturated bond. An epoxy group is preferably used as the thermosetting functional group. Moreover, you may use further the polymer which has no polymerization reactivity in itself.

  As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is suitably used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely.

The thermosetting binder used in the present invention is usually combined with a curing agent. As the curing agent, for example, a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid can be used, and one kind can be used alone, or two or more kinds can be mixed and used.
The compounding amount of the curing agent is usually in the range of 1 to 100 parts by weight, preferably 5 to 50 parts by weight per 100 parts by weight of the component containing the epoxy group (total amount of the binder epoxy compound and the polyfunctional epoxy compound). Part.

In order to improve the hardness and heat resistance of the cured layer, a catalyst capable of accelerating the thermosetting reaction between the acid and the epoxy may be added to the thermosetting binder. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used.
The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. As this thermal latent catalyst, for example, various compounds described in JP-A-4-218561 can be used.
The thermal latent catalyst is usually blended at a ratio of about 0.01 to 10.0 parts by weight with respect to a total of 100 parts by weight of the compound having two or more thermosetting functional groups in one molecule and the curing agent. .

The colored resin composition for a color filter according to the present invention contains a solvent for dispersing the pigment and dissolving the curable binder component. The solvent is not particularly limited as long as it is an organic solvent that does not react with each component in the resin composition and can dissolve or disperse them.
Examples of the solvent used in the resin composition of the present invention include cellosolve solvents, carbitol solvents, ester solvents, ketone solvents, carbitol acetate solvents, ether solvents, aprotic amide solvents, and lactone solvents. And organic solvents such as unsaturated hydrocarbon solvents and saturated hydrocarbon solvents. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl- One or more selected from the group consisting of 1-butyl acetate, 3-methoxybutyl acetate and cyclohexanone is preferable from the viewpoint of solubility of other components and coating suitability.

  In particular, when the colored resin composition of the present invention is used as an inkjet ink, the ink viscosity does not increase suddenly or clogging occurs, and the ejection performance is improved without adversely affecting the straightness and stability of ejection. Therefore, the boiling point is 180 ° C. to 260 ° C., particularly 210 ° C. to 260 ° C., and the vapor pressure at room temperature (particularly in the range of 18 ° C. to 25 ° C.) is 0.5 mmHg (66.7 Pa) or less, particularly 0.1 mmHg ( It is preferable to use a solvent component of 13.3 Pa) or less as the main solvent. For example, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, and diethyl succinate. It can be illustrated. The “main solvent” is a solvent that accounts for 50% by weight or more of the total amount of the solvent. The main solvent is desirably used in the highest possible blending ratio, specifically 70% by weight or more, preferably 90% by weight or more.

  While these main solvents are slow to dry, they are excellent in intermittent ejection properties in ink jets. On the other hand, since the drying is slow at the time of coating film formation, there may be a problem in production efficiency. In addition, a lower boiling solvent may be mixed. Other subsolvents preferably used in combination with the main solvent include, for example, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, ethyl acetate, ethanol, acetone and the like.

  In the colored resin composition for color filter of the present invention, a pigment derivative, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, Various additives such as an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter may be included.

(Mixing ratio of each component in the colored resin composition for color filter)
The content of the pigment (the total content of the pigment and the pigment derivative when a pigment derivative is included) is 5 to 65% by weight, more preferably 10 to 10%, based on the total solid content of the colored resin composition for color filters. It is preferable to mix at a ratio of 50% by weight. If the amount of the pigment is too small, there is a possibility that the transmission density when the colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 to 5.0 μm) may not be sufficient. There is a risk that the properties as a coating film such as adhesion to the substrate when the colored resin composition for color filter is applied and cured on the substrate, surface roughness of the cured film, coating film hardness, etc., Further, since the ratio of the amount of the dispersant used for dispersing the pigment in the colored resin composition for the color filter is increased, characteristics such as developability and heat resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Further, the total content of the pigment dispersant and the polymer dispersant is not particularly limited as long as the pigment can be uniformly dispersed. For example, the content of the colored resin composition for a color filter is not limited. It is preferably in the range of 1 to 50% by weight, particularly preferably in the range of 5 to 40% by weight, based on the total solid content. When the content is less than 1% by weight with respect to the total solid content of the colored resin composition for a color filter, it may be difficult to uniformly disperse the pigment, and the content exceeds 50% by weight. May cause a decrease in curability and developability.
The total amount of the curable binder component is preferably 24 to 94% by weight, and preferably 40 to 90% by weight, based on the total solid content of the colored resin composition for a color filter.
Further, the content of the solvent is not particularly limited as long as the colored layer can be accurately formed. Usually, it is preferably in the range of 65 to 95% by weight, more preferably in the range of 75 to 88% by weight, based on the total amount of the colored resin composition for a color filter containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

(Manufacture of colored resin composition for color filter)
As a method for producing a colored resin composition for a color filter, a pigment, a pigment dispersant, a polymer dispersant, a curable binder component, and various additive components used as desired are uniformly dissolved or dissolved in a solvent. Any method can be used as long as it can be dispersed, and it can be prepared by mixing using a known mixing means.
As a method for preparing the resin composition, for example, (1) the above-described pigment dispersion is prepared by adding the above-described polymer dispersant, pigment, and pigment dispersant in a solvent and dispersing the mixture using a disperser. After preparation, a method of adding and mixing a curable binder component and various additive components used as desired, (2) In the solvent, the above pigment, pigment dispersant, polymer dispersant, A method of simultaneously adding and mixing the curable binder component and various additive components used as desired; and (3) the above-described polymer dispersant, the curable binder component, and various types as required. Examples thereof include a method in which an additive component is added and mixed, and then a pigment and a pigment dispersant are added and mixed.
Among these methods, the method (1) is preferable from the viewpoint that the aggregation of the pigment can be effectively prevented and the pigment can be uniformly dispersed.

  In the preparation of the pigment dispersion in the above method (1), as a disperser for performing a pigment dispersion treatment, a roll mill such as a two-roll or a three-roll, a ball mill such as a ball mill or a vibration ball mill, a paint shaker, a continuous Examples thereof include a bead mill such as a disk type bead mill and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2 mm, more preferably 0.05 to 1 mm. Specifically, pre-dispersion is performed with 1 to 2 mm zirconia beads having a relatively large bead diameter, and further main dispersion is performed with 0.03 to 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a membrane filter of about 5.0 to 0.2 μm after dispersion. Thereby, the pigment dispersion liquid excellent in the dispersibility of a pigment is obtained.

4). Next, the color filter of the present invention will be described.
The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a colored resin composition for a color filter according to the present invention. It has a colored layer formed by curing a product.
The color filter of the present invention can be provided with a high-contrast colored layer without lowering the luminance by using the colored resin composition for a color filter of the present invention.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
The colored layer used in the color filter of the present invention is not particularly limited as long as it is formed by curing the above-described colored resin composition for a color filter of the present invention, but is usually on a transparent substrate described later. Depending on the type of pigment formed in the opening of the light-shielding portion and contained in the colored resin composition for color filter, it is composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the colored resin composition for a color filter, but is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed, for example, by the following method.
First, the above-described colored resin composition for a color filter of the present invention is applied onto a transparent substrate described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method. To form a wet paint film.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. And a coating film of a colored resin composition for a color filter. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition for the color filter to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution.
Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. This metal thin film may be a laminate of a CrOx film (x is an arbitrary number) and a Cr film, or a CrOx film (x is an arbitrary number) with a reduced reflectance, CrNy A film (y is an arbitrary number) and three layers of Cr films may be laminated.
When the light-shielding part is a material in which a black colorant is dispersed or dissolved in a binder resin, the method for forming the light-shielding part is not particularly limited as long as the light-shielding part can be patterned. For example, a photolithography method, a printing method, an ink jet method and the like using the light shielding part resin composition can be exemplified.

  In the above case, when a printing method or an inkjet method is used as a method for forming the light shielding portion, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxy Examples thereof include ethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin and the like.

  In the above case, when a photolithography method is used as a method for forming the light shielding portion, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive material. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the resin composition for a light shielding part containing a black pigment such as carbon black or titanium black as a pigment and a photosensitive resin, and further a sensitizer if necessary. Application improvers, development improvers, crosslinking agents, polymerization inhibitors, plasticizers, flame retardants, and the like may be added.

  On the other hand, when the light shielding part is a metal thin film, the method for forming the light shielding part is not particularly limited as long as the light shielding part can be patterned, and for example, photolithography, vapor deposition using a mask. Method, printing method and the like.

  The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case where a black colorant is dispersed or dissolved in a binder resin. Is set.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

5. Next, the liquid crystal display device of the present invention will be described.
The liquid crystal display device of the present invention includes the color filter of the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

6). Next, the organic light emitting display device of the present invention will be described.
The organic light emitting display device of the present invention includes the above-described color filter of the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

(Synthesis Example 1) Pigment dispersant 1
To 130 parts by weight of water, 5.20 parts by weight of p-aminobenzenesulfonic acid and 1.59 parts by weight of sodium carbonate are added, stirred and dissolved. Next, 5.53 parts by weight of cyanuric chloride was added, and the mixture was stirred at 20 ° C. for 1 hour. Next, 5.59 parts by weight of aniline was added and stirred at 80 to 90 ° C. for 2 hours. After cooling to room temperature, it was washed twice with 200 parts by weight of water. The wet cake was vacuum dried at 80 ° C. to obtain a white product. The molecular weight of the obtained target product (pigment dispersant 1 having the following structural formula) was confirmed by TOF-MS (manufactured by BRUKER, REFLEX II).

(Synthesis example 2) Pigment dispersant 2
The synthesis was carried out by changing 5.59 parts by weight of aniline of Synthesis Example 1 to 8.59 parts by weight of 1-aminonaphthalene, and by the same TOF-MS as described above, the target product (pigment dispersant having the following structural formula) was obtained. The molecular weight of 2) was confirmed.

(Synthesis Example 3) Pigment derivative 3
Synthesis was performed by changing 5.20 parts by weight of p-aminobenzenesulfonic acid in Synthesis Example 1 to 6.70 parts by weight of 5-amino-2-naphthalenesulfonic acid, and obtained by TOF-MS in the same manner as described above. The molecular weight of the target product (pigment dispersant 3 having the following structural formula) was confirmed.

(Synthesis Example 4) Pigment dispersant 4
To 130 parts by weight of water, 5.20 parts by weight of p-aminobenzenesulfonic acid and 1.59 parts by weight of sodium carbonate are added, stirred and dissolved. Next, 5.53 parts by weight of cyanuric chloride was added, and the mixture was stirred at 20 ° C. for 1 hour. Next, 4.11 parts by weight of 3-aminobenzoic acid and 1.59 parts by weight of sodium carbonate were added, and the mixture was stirred at 90 ° C. for 1-2 hours. Next, 2.79 parts by weight of aniline was added and stirred at 80 to 90 ° C. for 2 hours. After cooling to room temperature, it was washed twice with 200 parts by weight of water. The wet cake was vacuum dried at 80 ° C. to obtain a white product. Similarly to the above, the molecular weight of the obtained target product (pigment dispersant 4 having the following structural formula) was confirmed by TOF-MS.

(Synthesis Example 5) Comparative pigment dispersant 1
While cooling to 10 ° C., 120.0 parts by weight of 20% fuming sulfuric acid was stirred, and 12.0 parts by weight of Pigment Red 254 was added. Subsequently, it stirred at 63 degreeC for 6 hours. After cooling to room temperature, the reaction solution was added to 1200 parts by weight of ice water, and the precipitate was filtered. Subsequently, it was washed with 800 parts by weight of water and vacuum-dried at 80 ° C. to obtain a red product. In the same manner as above, the molecular weight of the obtained target product (Comparative Pigment Dispersant 1 having the following structural formula) was confirmed by TOF-MS.

(Synthesis Example 6) Comparative Pigment Dispersant 2
After adding 10.0 parts by weight of copper phthalocyanine to 266.7 parts by weight of 100% sulfuric acid, the mixture was stirred at 100 ° C. for 2 hours. After cooling to room temperature, the reaction solution was added to 800 parts by weight of ice water, and the precipitate was filtered. Subsequently, it was washed twice with 800 parts by weight of water and vacuum dried at 80 ° C. to obtain a blue product. Similarly to the above, the molecular weight of the obtained target product (Comparative Pigment Dispersant 2 having the following structural formula) was confirmed by TOF-MS.

(Production Example 1 Preparation of Polymer Dispersant Solution a)
In a 100 mL round bottom flask, 22.6 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added to a polymer dispersant (trade name: BYK-LPN6919, manufactured by Big Chemie, weight average molecular weight 7800, amine number 130, solid content 60 (Weight%) 2.2 parts by weight, 0.2 parts by weight of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.), and a block copolymer type dispersion formed by partial salt formation by ultrasonic treatment for 15 minutes A polymer dispersant solution a as an agent was obtained.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

Example 1
(1) Preparation of Pigment Dispersion Solution According to Production Example 1, 3.7 parts by weight of red pigment (CI Pigment Red 254 (PR254)) and 0.2 part by weight of Pigment Dispersant 1 as a pigment dispersant 25.0 parts by weight of the prepared polymer dispersant solution a and an alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer (molar ratio 30/40/10/20, acid value: 70 mgKOH / g, molecular weight 6000, solid content 44.1% by weight diluted with propylene glycol monomethyl ether acetate))) 2.0 parts by weight, mixed with 2 mm zirconia beads for 1 hour in a paint shaker, and further 0.1 mm zirconia Dispersion was performed with beads for 10 hours to obtain a red pigment dispersion A having a pigment concentration of 13%. The bead filling rate in the vessel at the time of dispersion was 50%.

  The viscosity of the prepared pigment dispersion was measured at 6 rpm with an Anton Paar rheometer MCR-301 (cone plate CP50-1, measured at 23 ° C.). The viscosity over time was remeasured with the dispersion stored at room temperature for 1 week. The dispersion stability was evaluated as ◯ when there was no increase in viscosity, and the dispersion stability was evaluated as x when there was a significant increase in viscosity.

(2) Preparation of red photosensitive resin composition for color filter To 4.06 parts by weight of the red pigment dispersion A obtained above, 2.22 parts by weight of the following binder composition and 3.72 parts by weight of propylene glycol monomethyl ether acetate , Surfactant R08MH (manufactured by DIC) 0.01 part by weight and silane coupling agent KBM503 (manufactured by Shin-Etsu Silicone) 0.05 part by weight are added and mixed, and pressure filtration is performed. A photosensitive resin composition was obtained.

<Binder composition>
Alkali-soluble resin (styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate copolymer (molar ratio 30/40/10/20, acid value: 70 mg KOH / g, molecular weight 6000)): 11.0 parts by weight Tetrafunctional acrylate monomer (trade name: Aronix M450, manufactured by Toagosei Co., Ltd.): 8.2 parts by weight / photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane -1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.): 1.0 part by weight-photopolymerization initiator (2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -1-butanone (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals): 2.4 parts by weight / photosensitization (4,4'-bis (dimethylamino) benzophenone): 0.7 parts by weight Solvent (propylene glycol monomethyl ether acetate): 43.2 parts by weight

(Evaluation results)
<Contrast, hue, and luminance evaluation>
The obtained red photosensitive resin composition for color filters was applied onto a 0.7 mm thick glass substrate (manufactured by Nippon Electric Glass Co., Ltd., “OA-10G”) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A photocured film (red colored layer) was obtained by exposure (60 mJ) using a small aligner. The cured film was heated in an oven at 230 ° C. for 30 minutes to obtain a cured film after post-baking. The film thickness after photocuring was adjusted so that the target chromaticity after post-baking would be x = 0.650.
Luminance was measured using a contrast measurement device CT-1 manufactured by Aisaka Electric Co., Ltd., light source: F10 lamp between cold cathodes, and luminance meter: LS-100 manufactured by Konica Minolta. The contrast can be derived from the following formula using the measured luminance value.
Contrast = parallel luminance (cd / m ² ) / orthogonal luminance (cd / m ² )
Hue (x, y) and luminance (Y) were measured using “Microspectroscope OSP-SP200” manufactured by Olympus Corporation.

(Examples 2 to 4)
In Example 1, except that pigment dispersant 1 was changed to pigment dispersants 2 to 4, respectively, a dispersion and a post-baked cured film were prepared in the same manner as in Example 1, and the viscosity of the dispersion, post The contrast of the cured film after baking was evaluated. The results are shown in Table 1.

(Comparative Example 1)
A dispersion and a post-baked cured film were prepared in the same manner as in Example 1 except that 3.9 parts by weight of the red pigment (PR254) was used without using the pigment dispersant, and the viscosity of the dispersion and the post-baking. The contrast of the postcured film was evaluated. The results are shown in Table 1.

(Comparative Example 2)
In Example 1, except that the pigment dispersant 1 was changed to the comparative pigment dispersant 1, a dispersion and a cured film after post-baking were prepared in the same manner as in Example 1, and the viscosity of the dispersion and post-baking The contrast of the cured film was evaluated. The results are shown in Table 1.

(Examples 5-6)
In Example 1, the red pigment (PR254) was changed to a blue pigment (C.I. Pigment Blue 15: 6 (PB15: 6)), and Example 5 was carried out using the same pigment dispersant 1 as in Example 1. In Example 6, a dispersion and a post-baked cured film were prepared in the same manner as in Example 1 except that the pigment dispersant 1 was changed to the pigment dispersant 3, and the viscosity of the dispersion and the post-baked cured film were prepared. The contrast was evaluated. The film thickness after photocuring was adjusted so that the target chromaticity after post-baking was y = 0.127. The results are shown in Table 2.

(Comparative Example 3)
A dispersion and a cured film after post-baking were prepared in the same manner as in Example 5 except that 3.9 parts by weight of the blue pigment (PB15: 6) was used without using the pigment dispersant, and the viscosity of the dispersion, The contrast of the post-baked cured film was evaluated. The results are shown in Table 2.

(Comparative Example 4)
In Example 5, except that the pigment dispersant 1 was changed to the comparative pigment dispersant 2, a dispersion and a cured film after post-baking were prepared in the same manner as in Example 5, and the viscosity of the dispersion and post-baking The contrast of the cured film was evaluated. The results are shown in Table 2.

In Examples 1 to 4 in which the pigment dispersants 1 to 4 according to the present invention are used together with the red pigment (PR254), the dispersibility and dispersion stability of the pigment are excellent, the hue and the luminance and contrast are not affected. An excellent red colored layer was obtained. In Examples 5 and 6 in which Pigment Dispersant 1 and Pigment Dispersant 3 were used for the blue pigment (PB15: 6), the dispersibility and dispersion stability of the pigment were excellent, and the hue was not affected. And the blue colored layer excellent in contrast was obtained.
On the other hand, in Comparative Example 1 and Comparative Example 3 in which no pigment dispersant was used, the dispersibility and dispersion stability of the pigment were poor, and the contrast of the resulting colored layer was also poor.
In Comparative Example 2, as the pigment dispersant for the red pigment (PR254), the comparative pigment dispersant 1, which is a pigment derivative having a structure in which a sulfo group is introduced into PR254, was used, so that the dispersibility and dispersion stability of the pigment were good. Although the contrast was excellent, the hue was turbid and the luminance was inferior compared with Examples 1-4.
In Comparative Example 4, as the pigment dispersant of the blue pigment (PB15: 6), the comparative pigment dispersant 2, which is a pigment derivative having a structure in which a sulfo group is introduced into PB15: 6, was used. Although it was good and the contrast was excellent, the hue was turbid and the luminance was inferior as compared with Examples 5 and 6.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims (8)

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

(In General Formula (1), R ^{1 to} R ³ are each independently a 1-3 ring aryl group which may have a substituent, and may be the same or different. R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a carboxyalkyl group or a sulfoalkyl group, and R ⁵ is a linear or branched alkyl group having 1 to 20 carbon atoms, carboxyalkyl. M represents the number of sulfo groups, n represents the number of sulfonamido groups, and at least one sulfo group or sulfonamido group is bonded to at least one of R ^{1 to} R ^3. M and n are each independently an integer of 0 or more, and m + n is an integer of 1 to 9.) The substituent that R ^{1 to} R ³ may have is one or more substituents selected from the group consisting of an alkyl group, an alkoxy group, a halogen atom, a carboxyl group, and a hydroxyl group. The pigment dispersant as described.   A pigment dispersion containing a pigment, the pigment dispersant according to claim 1, a polymer dispersant, and a solvent.   The pigment dispersion according to claim 3, wherein the polymer dispersant is a basic polymer dispersant.   A colored resin composition for a color filter, comprising the pigment dispersion according to claim 3 or 4 and a curable binder component.   A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is formed by curing the colored resin composition for a color filter according to claim 5. A color filter comprising a colored layer formed by the method.   A liquid crystal display device comprising: the color filter according to claim 6; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.   An organic light emitting display device comprising the color filter according to claim 6 and an organic light emitter.

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