JP2016122073A - Color material dispersion liquid, photosensitive coloring 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 color material dispersion liquid with which a photosensitive coloring resin composition can be manufactured having excellent color material dispersion stability, suppressing the generation of a development residue, and having excellent development adhesion and solvent resolubility.SOLUTION: There is provided a color material dispersion liquid containing a color material, dispersant, and solvent, where the dispersant is at least one of a block copolymer (P1) containing at least one of (i) a constitutional unit derived from a hydroxyl group-containing monomer and a constitutional unit derived from an aromatic group-containing monomer and (ii) a constitutional unit derived from a hydroxyl group and an aromatic group-containing monomer, and a salt-block copolymer (P2) in which at least a part of a nitrogen portion of a terminal included in the constitutional unit of the block copolymer (P1) has formed a salt; the dispersant has an amine value of 35 to 110 mgKOH/g and a glass transition temperature of 30°C or higher.SELECTED DRAWING: None

Description

  The present invention relates to a color material dispersion, a photosensitive 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 mobile displays (cell phones, smartphones, tablet PCs) 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, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. As a light source at that time, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. In the organic light emitting display device, a color filter is used for color adjustment.
Under such circumstances, demands for higher luminance, higher contrast, and improved color reproducibility are increasing in color filters.

  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 pixels in a color filter, among others, a pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, and the like.
In a color filter having pixels formed by using a pigment dispersion method, miniaturization of pigments is being studied in order to achieve high brightness and high contrast. By making the pigment finer, it is considered that the scattering of light transmitted through the color filter by the pigment particles is reduced, and high brightness and high contrast are achieved.
However, since the refined pigment particles tend to aggregate, there is a problem that the dispersibility and dispersion stability are lowered.

  It is known that a dispersant is effective as a technique for improving the dispersibility of the finely divided pigment. For example, Patent Document 1 discloses dialkylamino (meth) for the purpose of providing a pigment dispersion for a color filter that can form a cured film excellent in contrast, has low viscosity, and is excellent in storage stability. It has a structural unit derived from acrylamide and a structural unit derived from alkoxy polyalkylene glycol (meth) acrylate, and has a quaternization rate (of quaternary ammonium groups relative to the total number of molar equivalents of tertiary amino groups and quaternary ammonium groups). A pigment dispersant having a molar equivalent number ratio of 10 to 80 mol% is described.

  Further, Patent Document 2 discloses a dispersion aiming to obtain a colored layer which has high brightness but has low heat resistance compared to a pigment and which has improved heat resistance even when a triarylmethane dye lake colorant is used. In the liquid and colored resin composition, as one dispersant, a graft copolymer having a structural unit derived from a dialkylamino (meth) acrylamide and a structural unit derived from a macromonomer, derived from the dialkylamino (meth) acrylamide Dispersants are disclosed in which the tertiary amino group of the structural unit forms a salt with an acidic organophosphorus compound. In Patent Document 2, when a color material obtained by combining a triarylmethane dye with a specific anion and a specific dispersant is used, not only the dispersibility and dispersion stability of the color material are improved. Furthermore, it is described that the obtained colored layer is also excellent in heat resistance.

International Publication No. 2014/10687 JP 2013-250446 A

In recent color filters, it is necessary to solve various problems in mass production of color filters in accordance with the technology for improving the colorant dispersibility in order to realize the demand for higher brightness and higher contrast. . That is, in order to increase the color material concentration in the resin composition, it is necessary to increase the amount of the dispersant, which causes problems such as generation of a development residue and a delay in development time. Further, when the colorant concentration is increased and the dispersant content is increased, the amount of the binder is relatively decreased, which causes a problem that the colored resin layer is easily peeled off from the base substrate during development. Therefore, although it is calculated | required that it has high image development adhesiveness as a colored resin composition, there existed a problem that it did not reach a practical use level. Furthermore, in the manufacturing process of a color filter, it is calculated | required that the solid content of the colored resin composition once dried is excellent in the property which melt | dissolves in a solvent again, and the re-solubility in a solvent. For example, if the photosensitive colored resin composition adheres to the tip of the die lip when coating with a die coater, a solidified product is generated by drying, but the solidified product dissolves in the photosensitive colored resin composition when coating is resumed. If it is not easy to do, a part of the solidified product on the die lip peels off and easily adheres to the colored layer of the color filter, which causes a foreign matter defect. In particular, when the colorant concentration of the colored resin composition is increased, the solvent re-solubility is likely to be insufficient, and the yield is reduced due to the occurrence of the foreign matter in the color filter manufacturing process.
However, even with the copolymers described in Patent Documents 1 and 2, in addition to color material dispersion stability, various problems in mass production of color filters, development residue generation, development adhesion, solvent re-use It was difficult to solve all of the solubility, as shown in Comparative Examples described later.

  The present invention has been made in view of the above circumstances, and a photosensitive colored resin composition having excellent colorant dispersion stability and excellent development adhesion and solvent resolubility while suppressing generation of development residues. Color filter capable of forming a colored layer with excellent colorant dispersion, excellent colorant dispersion stability, excellent development adhesion and solvent re-dissolution, and excellent contrast while suppressing development residue generation Photosensitive coloring resin composition, color filter formed using the photosensitive coloring resin composition for color filter, liquid crystal display device excellent in display characteristics by using the color filter, and organic light emitting display device The purpose is to provide.

The color material dispersion according to the present invention is a color material dispersion containing a color material, a dispersant, and a solvent,
The dispersant is at least one of the following block copolymer (P1) and the following salt-type block copolymer (P2),
P1: a block copolymer containing a structural unit represented by the following general formula (I);
P2: From the compounds represented by the following general formulas (1) to (3) and at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer (P1) A salt-type block copolymer in which a salt is formed with one or more compounds selected from the group consisting of:
The block copolymer (P1) has an amine value of 35 to 110 mgKOH / g, and the dispersant has a glass transition temperature of 30 ° C. or higher.

（一般式（Ｉ）中、Ｒ^１及びＲ^１’はそれぞれ独立に、水素原子又はメチル基、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^２及びＲ^３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２及びＲ^３が互いに結合して環構造を形成してもよい。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、ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。
一般式（１）において、Ｒ^ａは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｅを表し、Ｒ^ｅは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表す。一般式（２）において、Ｒ^ｂ、Ｒ^ｂ’、及びＲ^ｂ”はそれぞれ独立に、水素原子、酸性基又はそのエステル基、置換基を有してもよい炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｆを表し、Ｒ^ｆは、置換基を有してもよい炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表し、Ｘは、塩素原子、臭素原子、又はヨウ素原子を表す。一般式（３）において、Ｒ^ｃ及びＲ^ｄはそれぞれ独立に、水素原子、水酸基、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｅを表し、Ｒ^ｅは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表す。但し、Ｒ^ｃ及びＲ^ｄの少なくとも一つは炭素原子を含む。）

(In General Formula (I), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, — [CH (R ⁶ ) —CH (R ⁷ ) A divalent group represented by —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or [(CH ₂ ) _y —O] _z — (CH ₂ ) _y —, R ² and R ³ are: Each independently represents a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ² and R ³ may be bonded to each other to form a ring structure, and R ⁶ and R ⁷ are each independently A hydrogen atom or a methyl group, 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.
In General Formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R. ^e represents, and R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or an alkylene having 1 to 4 carbon atoms. It represents a (meth) acryloyl group via a group. In the general formula (2), R ^b , R ^{b ′} , and R ^{b ″} each independently represent a hydrogen atom, an acidic group or an ester group thereof, a linear chain having 1 to 20 carbon atoms that may have a substituent, Represents a branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or -O- ^Rf , and ^Rf has a substituent. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or 1 carbon atom Represents a (meth) acryloyl group via an alkylene group of ˜4, X represents a chlorine atom, a bromine atom, or an iodine atom, In the general formula (3), R ^c and R ^d are each independently a hydrogen atom; , A hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Represents a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, A phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms, provided that at least one of R ^c and R ^d contains a carbon atom. .)

  Moreover, the photosensitive colored resin composition for a color filter according to the present invention contains the color material dispersion according to the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. .

  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 is the color filter photosensitivity according to the present invention. It is a colored layer formed by curing a colored resin composition.

The present invention provides a liquid crystal display device comprising the color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
The present invention also provides an organic light emitting display device comprising the color filter according to the present invention and an organic light emitter.

  According to the present invention, a colorant dispersion liquid, which is excellent in colorant dispersion stability and capable of producing a photosensitive colored resin composition excellent in development adhesion and solvent resolubility while suppressing generation of development residues, and color A photosensitive colored resin composition for a color filter, which is excellent in material dispersion stability and has excellent development adhesion and solvent resolubility while being able to form a colored layer with excellent contrast while suppressing the occurrence of development residues, A color filter formed using a photosensitive colored resin composition for a color filter, and a liquid crystal display device and an organic light emitting display device excellent in display characteristics can be provided by using the color filter.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention.

Hereinafter, the color material dispersion, the photosensitive colored resin composition for color filter, the color filter, the liquid crystal display device, and the organic light emitting display device according to the present invention will be described in detail 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 represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.

[Colorant dispersion]
The color material dispersion according to the present invention is a color material dispersion containing a color material, a dispersant, and a solvent,
The dispersant is at least one of the following block copolymer (P1) and the following salt-type block copolymer (P2),
P1: a block copolymer containing a structural unit represented by the following general formula (I);
P2: From the compounds represented by the following general formulas (1) to (3) and at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer (P1) A salt-type block copolymer in which a salt is formed with one or more compounds selected from the group consisting of:
The block copolymer (P1) has an amine value of 35 to 110 mgKOH / g, and the dispersant has a glass transition temperature of 30 ° C. or higher.

（一般式（Ｉ）中、Ｒ^１及びＲ^１’はそれぞれ独立に、水素原子又はメチル基、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^２及びＲ^３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２及びＲ^３が互いに結合して環構造を形成してもよい。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、ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。
一般式（１）において、Ｒ^ａは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｅを表し、Ｒ^ｅは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表す。一般式（２）において、Ｒ^ｂ、Ｒ^ｂ’、及びＲ^ｂ”はそれぞれ独立に、水素原子、酸性基又はそのエステル基、置換基を有してもよい炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｆを表し、Ｒ^ｆは、置換基を有してもよい炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表し、Ｘは、塩素原子、臭素原子、又はヨウ素原子を表す。一般式（３）において、Ｒ^ｃ及びＲ^ｄはそれぞれ独立に、水素原子、水酸基、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは−Ｏ−Ｒ^ｅを表し、Ｒ^ｅは、炭素数１〜２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１〜４のアルキレン基を介した（メタ）アクリロイル基を表す。但し、Ｒ^ｃ及びＲ^ｄの少なくとも一つは炭素原子を含む。）

(In General Formula (I), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, — [CH (R ⁶ ) —CH (R ⁷ ) A divalent group represented by —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or [(CH ₂ ) _y —O] _z — (CH ₂ ) _y —, R ² and R ³ are: Each independently represents a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ² and R ³ may be bonded to each other to form a ring structure, and R ⁶ and R ⁷ are each independently A hydrogen atom or a methyl group, 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.
In General Formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R. ^e represents, and R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or an alkylene having 1 to 4 carbon atoms. It represents a (meth) acryloyl group via a group. In the general formula (2), R ^b , R ^{b ′} , and R ^{b ″} each independently represent a hydrogen atom, an acidic group or an ester group thereof, a linear chain having 1 to 20 carbon atoms that may have a substituent, Represents a branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or -O- ^Rf , and ^Rf has a substituent. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or 1 carbon atom Represents a (meth) acryloyl group via an alkylene group of ˜4, X represents a chlorine atom, a bromine atom, or an iodine atom, In the general formula (3), R ^c and R ^d are each independently a hydrogen atom; , A hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Represents a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, A phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms, provided that at least one of R ^c and R ^d contains a carbon atom. .)

As a result of intensive studies, the inventors of the present invention have found that if the amine value of a specific block copolymer is low, the colorant dispersion stability and the contrast of the colored layer do not reach practical levels, and if the amine value is too high, the solvent resolubility is high. However, it has been found that when the amine value is a specific value, the colorant dispersion stability and the contrast of the colored layer are improved, and the solvent resolubility is improved.
The colorant dispersion of the present invention has, as a dispersant, a block copolymer (P1) containing the structural unit represented by the general formula (I) having the specific amine value and the specific glass transition temperature, and Since at least one salt-type block copolymer (P2) in which the block copolymer and the specific compound form a salt is used, the color material dispersibility and the color material dispersion stability are excellent. Even when the dispersant content relative to the color material is smaller than that of the conventional dispersant, the color material has excellent color material dispersibility and color material dispersion stability. It has also been found that even when a pigment that has been difficult to disperse in the past is used, not only the dispersibility and dispersion stability are increased, but also there is an effect of improving luminance and heat resistance. Furthermore, in the case of having the specific dispersant for a pigment that is likely to precipitate a pigment aggregate when subjected to a heating process at a high temperature after fine dispersion, it has an effect of suppressing the precipitation of the pigment aggregate. I also found that there is.
The structural unit represented by the general formula (I) has a basic nitrogen moiety (—NR ² R ³ ) corresponding to an amino group, and further has an amide group, and thus has high basicity. . In addition, the block copolymer (P1) containing the structural unit represented by the general formula (I) has an amine value larger than a specific value, so that the high basic portion is sufficiently adsorbed to the colorant. It is presumed that the adsorbability with respect to the color material and the maintenance ability after the adsorption are particularly enhanced, and the color material dispersibility and the color material dispersion stability are excellent. On the other hand, since it has an amine value smaller than a specific value, the polarity is not too strong, and it is estimated that the colorant dispersibility and the colorant dispersion stability are improved without impairing the solvent resolubility. The
The coloring material is stabilized by appropriately adsorbing the dispersing agent on the surface which is finely exposed through the dispersing step and exposed.
However, when the color material applied to the substrate is subjected to a high temperature of about 230 ° C. in the color filter manufacturing process, the adsorptivity of the dispersant adsorbed on the color material becomes weak due to thermal motion and is partially detached. It is estimated that. As a result, the surface of the color material from which the dispersant is detached and exposed becomes an environment in which the crystallinity of the color material is likely to change (transfer, grow, etc.).
On the other hand, since the structural unit represented by the general formula (I) has a strong basicity, it has a strong adsorptivity to the coloring material and a maintenance ability after adsorption. Therefore, even when a high temperature of about 230 ° C. is applied in the color filter manufacturing process, the detachment from the color material is remarkably reduced, and as a result, the surface of the color material is maintained in a stable state, It is presumed that a decrease in luminance can be suppressed. Further, it is presumed that precipitation of aggregates can be suppressed in a color material in which pigment aggregates easily precipitate.

In addition, the coloring material dispersion of the present invention can produce a photosensitive colored resin composition having excellent development adhesion and solvent resolubility while suppressing generation of development residues.
Conventionally, a block copolymer containing the structural unit represented by the above general formula (I) has been known as a pigment dispersant (Patent Document 1). When the described copolymer was used as a pigment dispersant, the development adhesiveness did not reach a practical level. In the pigment dispersant described in Patent Document 1, as shown in a comparative example to be described later, since the copolymer contains a structural unit derived from an alkoxypolyalkylene glycol (meth) acrylate containing a polyalkyleneoxy chain, glass is used. It is presumed that the transition temperature is lowered. When the glass transition temperature of the copolymer as the pigment dispersant is lower than the developer temperature, it is presumed that the molecular motion of the dispersant increases during development, and as a result, the development adhesion decreases.

On the other hand, even if the specific block copolymer or salt-type block copolymer has the specific amine value, if the glass transition temperature is lower than the predetermined value, the development adhesion does not reach a practical level. It has been found that when a block copolymer or a salt type block copolymer having a temperature of 30 ° C. or higher, which is higher than the developer temperature, is used, the development adhesiveness is excellent. When a block copolymer or salt type block copolymer having a glass transition temperature of 30 ° C. or higher, which is higher than the developer temperature, is used, molecular movement of the dispersant during development is suppressed, resulting in a decrease in development adhesion. Is estimated to be suppressed.
In addition, the specific block copolymer or salt-type block copolymer has excellent colorant dispersibility and colorant dispersion stability even if the dispersant content is smaller than that of conventional dispersants. Even if the colorant concentration in the resin composition is increased, the dispersant content can be kept low, and the binder component content contained in the photosensitive coloring composition can be relatively increased. Stain generation can be suppressed. The water stain refers to this phenomenon in which a trace of water stain is generated after rinsing with pure water after alkali development. Such water stain disappears after post-baking, so there is no problem as a product, but it is detected as unevenness in the appearance inspection of the patterning surface after development, and there is a problem that it is impossible to distinguish between normal products and abnormal products. Arise. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.
Furthermore, as described above, by setting the amine value to a specific value or less, the polarity does not become too strong, and the solvent resolubility becomes good.

The color material dispersion of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components as long as the effects of the present invention are not impaired. .
Hereinafter, each component of the color material dispersion of the present invention will be described in detail in order from the dispersant characteristic of the present invention.

<Dispersant>
In the present invention, the dispersant is at least one of the block copolymer (P1) and the salt type block copolymer (P2), and the amine value of the block copolymer (P1) is A dispersant having a glass transition temperature of 30 ° C. or higher at 35 to 110 mg KOH / g is used.

The structural unit represented by the general formula (I) has basicity and functions as an adsorption site for a coloring material. Further, at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and one or more compounds selected from the group consisting of the general formulas (1) to (3) are salts. In this case, the salt forming part functions as a stronger adsorption site for the coloring material. Since the structural unit represented by the general formula (I) contains an amide bond, it is highly basic, and it is presumed that the adsorption function for the coloring material is further enhanced.
In the block copolymer used as the dispersant of the present invention, usually, a block containing the structural unit represented by the general formula (I) (hereinafter also referred to as A block) and a block having solvophilicity (Hereinafter also referred to as B block). The block copolymer having such a structure functions as a colorant dispersant by sharing the function between the colorant and the adsorbing A block and the solvophilic B block.

[Block copolymer]
{A block}
(Structural unit represented by general formula (I))
In general formula (I), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group. R ¹ is preferably a methyl group from the viewpoint of compatibility with other components.
A represents 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 —.
The alkylene group having 1 to 8 carbon atoms in A may be linear or branched. For example, methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various types. Xylene group, various octylene groups and the like. R ⁵ and R ⁶ 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.
As A, an alkylene group having 1 to 8 carbon atoms is preferable from the viewpoint of dispersibility, and among them, A is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group.

Examples of the hydrocarbon group in the hydrocarbon group that may include a hetero atom in R ² and R ³ include an alkyl group, an aralkyl group, and an aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and the like. 1-18 are preferable and, among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for the carbon atom number of an aralkyl group, 7-14 are more preferable.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for the carbon atom number of an aryl group, 6-12 are more preferable. The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is replaced with a hetero atom. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
Moreover, the hydrogen atom in a hydrocarbon group may be substituted by halogen atoms, such as a C1-C5 alkyl group, a fluorine atom, a chlorine atom, and a bromine atom.

The phrase “R ² and R ³ are bonded to each other to form a ring structure” means that R ² and R ³ form a ring structure through a nitrogen atom. The ring structure formed by R ² and R ³ may contain a hetero atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring. In the present invention, those having a cyclic amine structure are also included in the name of an amino group (—NR ² R ³ ).

In the present invention, among them, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ³ are bonded to form a pyrrolidine ring, It is preferable to form a piperidine ring or a morpholine ring. Furthermore, it is preferable that R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms, which is excellent in dispersion stability.

Examples of the structural unit represented by the general formula (I) include alkyl group-substituted amino group-containing (meth) such as dimethylaminoethyl (meth) acrylamide and dialkylaminoalkyl (meth) acrylamide such as dimethylaminopropyl (meth) acrylamide. Although acrylamide etc. are mentioned, it is not limited to these. From the viewpoint of compatibility with other components, alkyl group-substituted amino group-containing methacrylamide such as dialkylaminoalkylmethacrylamide is preferred.
The structural unit represented by the general formula (I) may be composed of one type or may include two or more types of structural units.

  In the A block including the structural unit represented by the general formula (I), it is preferable that three or more structural units represented by the general formula (I) are included. Especially, from the point which improves a dispersibility and dispersion stability, it is preferable to contain 3-100 pieces, It is more preferable to contain 3-50 pieces, Furthermore, it is more preferable to contain 3-30 pieces.

The A block may have a structural unit other than the structural unit represented by the general formula (I) as long as the object of the present invention is achieved, and may share the structural unit represented by the general formula (I). Any polymerizable structural unit can be contained. For example, as the structural unit other than the structural unit represented by the general formula (I) that the A block part may contain, for example, a general formula such as alkyl group-substituted amino group-containing (meth) acrylate, 1-vinylimidazole, etc. A structural unit having a basic group other than the structural unit represented by (I) or a structural unit mentioned in the B block described later can be used. Specifically, for example, in the general formula (II) described later Examples of the structural unit are as follows.
In the A block in the block copolymer before salt formation, the content of the structural unit represented by the general formula (I) is 50 to 100% by mass with respect to the total mass of all the structural units of the A block. Is preferable, more preferably 80 to 100% by mass, and most preferably 100% by mass. This is because as the proportion of the structural unit represented by the general formula (I) is higher, the adsorptive power to the coloring material is improved, and the dispersibility and dispersion stability of the block copolymer are improved. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining A block which has a structural unit represented by general formula (I).

In the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is such that the amine value of the block copolymer before salt formation is within the range of the specific amine value. Although it is not particularly limited as long as it is appropriately set as described above, it is 5 to 60% by mass based on the total mass of all the structural units of the block copolymer before salt formation from the viewpoint of good dispersibility and dispersion stability. It is preferable that it is 10-50 mass%. In addition, the content rate of each structural unit in the said block copolymer is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation.
In addition, the structural unit represented by general formula (I) should just have affinity with a color material, may consist of 1 type, and may contain 2 or more types of structural units. Good.

{B block}
The B block does not contain the structural unit represented by the general formula (I) and functions as a solvophilic site. As the B block, among monomers having an unsaturated double bond that can be copolymerized with the monomer that derives the structural unit represented by the general formula (I), an appropriate solvent is used depending on the solvent. It is preferable to select and use. As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23 ° C. is 20 (g / 100 g solvent) or more with respect to the solvent used in combination.

The B block includes a structural unit that improves the solvophilicity appropriately selected according to the solvent used from the viewpoint of improving the solvophilicity.
Examples of the structural unit constituting the B block include a monomer having an unsaturated double bond copolymerizable with the monomer that derives the structural unit represented by the general formula (I). The structural unit represented by (II) is preferred.

（一般式（ＩＩ）中、Ａ’は、直接結合又は２価の連結基、Ｒ^４は、水素原子又はメチル基、Ｒ^５は、炭化水素基、−［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、炭化水素基、−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原子数１〜５のアルキル基である。
上記炭化水素基は、置換基を有していてもよい。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In General Formula (II), A ′ is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ is a monovalent group, and R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or a carbon atom having 1 to 5 carbon atoms. It is an alkyl group.
The hydrocarbon group 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. )

In the general formula (II), A ′ is a direct bond or a divalent linking group. The direct bond means that A ′ has no atom, that is, C (carbon atom) in the general formula (II) and R ⁵ are bonded without interposing another atom.
Examples of the divalent linking group for A ′ include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, and an ether group having 1 to 10 carbon atoms (—R′— OR ″-: R ′ and R ″ each independently represents an alkylene group), combinations thereof, and the like.
Among these, from the viewpoint of dispersibility, A ′ in General Formula (II) is preferably a divalent linking group containing a direct bond, a —CONH— group, or a —COO— group.

In the general formula (II), R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ^8. Indicates.
The hydrocarbon group for R ⁵ is preferably 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.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, 2 -Ethylhexyl group, 2-ethoxyethyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like can be mentioned.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. 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 aliphatic hydrocarbon substituent such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent. 6-24 are preferable and, as for the carbon atom number of an aryl group, 6-12 are more preferable.
Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, Furthermore, you may have a substituent. 7-20 are preferable and, as for the carbon atom 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 number of carbon atoms does not include the number of carbon atoms of the substituent.

In the above R ⁵ , x is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2, and y is an integer of 1-5, preferably an integer of 1-4, more preferably. Is 2 or 3. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.

The hydrocarbon group for R ⁸ can be the same as that shown for R ⁵ .
R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be linear, branched, or cyclic.
Moreover, R ⁵ in the structural unit represented by the general formula (II) may be the same or different from each other.

The R ⁵ is preferably selected so as to have excellent compatibility with the solvent described later. Specifically, for example, the solvent is generally used as a solvent for the colored resin composition for color filters. In the case of using a glycol ether acetate type, ether type, ester type solvent or the like, a methyl group, an ethyl group, an isobutyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group, or the like is preferable.

Furthermore, R ⁵ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, or an isocyanate group as long as the dispersion performance of the block copolymer is not hindered. After the synthesis of the polymer, the substituent may be added by reacting with the compound having the substituent.

  The number of structural units constituting the B block is not particularly limited, but is 10 to 300 from the viewpoint that the solvophilic portion and the parent color material portion act effectively and improve the dispersibility of the color material. Preferably, it is 10 to 100, more preferably 10 to 70.

  In the B block in the block copolymer, the content ratio of the structural unit represented by the general formula (II) is based on the total mass of all the structural units of the B block from the viewpoint of improving the solvent affinity and the colorant dispersibility. On the other hand, it is preferable that it is 50-100 mass%, and it is more preferable that it is 70-100 mass%. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining B block.

  Moreover, the content ratio of the structural unit represented by the general formula (II) in the block copolymer before salt formation is the total composition of the block copolymer before salt formation from the viewpoint of improving colorant dispersibility. It is preferable that it is 40-95 mass% with respect to the total mass of a unit, and it is more preferable that it is 50-90 mass%. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation.

  In the B block, the structural unit may be appropriately selected so as to function as a solvophilic moiety, and the structural unit represented by the general formula (II) may be composed of one kind, or two or more kinds. The structural unit may be included. Two or more structural units included in the B block may be randomly arranged in the block.

In the present invention, it is preferable that a structural unit derived from a hydroxyl group-containing monomer is contained in the B block of the block copolymer from the viewpoint of improving development adhesion and development speed. When a structural unit derived from a hydroxyl group-containing monomer is included, it tends to interact with glass, metal or the like that is usually used as a substrate, so that development adhesion is improved and affinity with an alkaline developer is improved. The development speed is considered to be improved.
Here, the hydroxyl group means an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As the structural unit derived from a hydroxyl group-containing monomer, a monomer containing an unsaturated double bond and a hydroxyl group that can be copolymerized with a monomer that derives the structural unit represented by formula (I) can be used. Examples of such monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin mono (meth). Examples thereof include acrylate, polyethylene glycol mono (meth) acrylate, ε-caprolactone 1-mol adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.
From the viewpoint of improving developability, it is more preferable to have a primary hydroxyl group than to have a secondary hydroxyl group. The primary hydroxyl group refers to a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the secondary hydroxyl group refers to a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a secondary carbon atom.
As will be described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving the development adhesion, among others, the value of the glass transition temperature of each monomer homopolymer (Tgi) is It is preferable to use a hydroxyl group-containing monomer that is 0 ° C. or higher, and it is preferable to use a hydroxyl group-containing monomer that is 10 ° C. or higher.
As a hydroxyl group-containing monomer having a glass transition temperature value (Tgi) of a monomer homopolymer of 10 ° C. or higher, 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxy are used from the viewpoint of improving development adhesion. It is preferably at least one selected from the group consisting of propyl (meth) acrylate.

  In the block copolymer (P1) before salt formation, the content ratio of the structural unit derived from the hydroxyl group-containing monomer is based on the total mass of all the structural units of the block copolymer from the viewpoint of improving development adhesion. 1 to 70% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, and particularly preferably 4 to 40% by mass. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the block copolymer before salt formation.

Moreover, in this invention, it is preferable from the point which the solvent resolubility improves that the structural unit derived from an aromatic group containing monomer is contained in B block. In the case where a structural unit derived from an aromatic group-containing monomer is included, compatibility with the solvent and other components is likely to be improved, so that it is considered that the solvent resolubility is improved.
As the structural unit derived from the aromatic group-containing monomer, a monomer containing an unsaturated double bond and an aromatic group that can be copolymerized with the monomer that derives the structural unit represented by the general formula (I) can be used. . Examples of such a monomer include acrylates such as benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and phenoxyethyl (meth) acrylate, styrenes such as styrene, and vinyl ethers such as phenyl vinyl ether. Kind.
As will be described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving the development adhesion, among others, the value of the glass transition temperature of each monomer homopolymer (Tgi) is It is preferable to use an aromatic group-containing monomer having a temperature of 0 ° C. or higher, and it is preferable to use an aromatic group-containing monomer having a temperature of 10 ° C. or higher.
From the viewpoint that re-solubility is easily improved, among them, it is at least one selected from the group consisting of benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and phenoxyethyl (meth) acrylate. It is preferable that it is at least one selected from the group consisting of benzyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  In the block copolymer (P1) before salt formation, the content ratio of the structural unit derived from the aromatic group-containing monomer is the total mass of all the structural units of the block copolymer from the viewpoint of improving solvent resolubility. Is preferably 1 to 70% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, and particularly preferably 4 to 40% by mass. preferable.

  Among them, the B block having solvophilic properties is composed of (i) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer, and (ii) a structural unit derived from a hydroxyl group and an aromatic group-containing monomer. The inclusion of at least one kind is preferred from the viewpoint of improving the development adhesion and solvent re-solubility.

  (I) When the structural unit derived from a hydroxyl group-containing monomer and the structural unit derived from an aromatic group-containing monomer are included, the structural unit derived from a hydroxyl group-containing monomer with respect to 1 part by mass of the structural unit derived from the aromatic group-containing monomer Is preferably contained in an amount of 0.15 parts by mass or more, more preferably 0.5 parts by mass or more. It is because it can be set as the thing excellent in image development adhesiveness as it is more than the said lower limit. Similarly, the structural unit derived from the hydroxyl group-containing monomer is preferably contained in an amount of 15 parts by mass or less, more preferably 7 parts by mass or less, with respect to 1 part by mass of the structural unit of the aromatic group-containing monomer. It is because it can be excellent in solvent resolubility that it is below the above-mentioned upper limit. Among them, the glass transition temperature value (Tgi) of the homopolymer is 10 parts per 1 part by mass of the structural unit derived from the aromatic group-containing monomer having a glass transition temperature value (Tgi) of the homopolymer of 10 ° C. or more. It is particularly preferable that the structural unit derived from a hydroxyl group-containing monomer having a temperature of not lower than ° C. is contained in the above range. It is because the development adhesiveness can be further improved by containing at the above lower limit or more, and the solvent resolubility can be further improved by containing at the above upper limit or less.

Examples of (ii) hydroxyl group and aromatic group-containing monomer in the structural unit derived from the hydroxyl group and aromatic group-containing monomer include 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl- Examples include 2-hydroxyethyl-phthalic acid. 2-Hydroxy-3-phenoxypropyl (meth) acrylate has a homopolymer having a glass transition temperature value (Tgi) of 10 ° C. or higher, an effect obtained from a structural unit derived from a hydroxyl group-containing monomer, and aromaticity. It is preferably used since any of the effects obtained from the structural unit derived from the group-containing monomer can be obtained. That is, it is preferable in that the development adhesion, the development speed, and the solvent resolubility are improved.
(Ii) When a structural unit derived from a hydroxyl group and aromatic group-containing monomer is included, the development adhesion, development speed, and solvent resolubility can be improved by one structural unit. There is also an advantage that the introduction ratio can be increased.

Moreover, in this invention, it is preferable from the point which improves the developability and the inhibitory effect of a development residue that the structural unit derived from a carboxy-group containing monomer is contained in B block of a block copolymer.
As the carboxy group-containing monomer used in the present invention, a monomer containing an unsaturated double bond and a carboxy group that can be copolymerized with a monomer that derives the structural unit represented by formula (I) can be used.
Examples of such monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use acid anhydride group containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the block copolymer (P1) before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer is appropriately set so that the acid value of the block copolymer is within the specific acid value range. However, it is preferably 0.05 to 4.5% by mass, and preferably 0.07 to 3.7% by mass with respect to the total mass of all the structural units of the block copolymer before salt formation. % Is more preferable.
In addition, the structural unit derived from a carboxy group-containing monomer may be composed of one kind or may contain two or more kinds of structural units.

  Further, as described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and the glass transition temperature value (Tgi) of the monomer homopolymer is 10 from the viewpoint of improving the development adhesion. It is preferable that the monomer having a temperature of 0 ° C. or higher is 75% by mass or more in the B block in total, and more preferably 85% by mass or more.

  In the block copolymer (P1), the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. It is preferable that it is in the range of 0.1 to 1.0 from the viewpoint of dispersibility and dispersion stability of the coloring material.

Moreover, the amine value of the block copolymer (P1) before salt formation is 35 mgKOH / g or more as a lower limit from the viewpoint of colorant dispersibility and dispersion stability. Among these, from the viewpoint of more excellent dispersion stability, the amine value of the block copolymer before salt formation is more preferably 40 mgKOH / g or more, and even more preferably 50 mgKOH / g or more. Moreover, the amine value of the block copolymer before salt formation is 110 mgKOH / g or less as an upper limit from the point of solvent resolubility. Among them, the amine value of the block copolymer before salt formation is more preferably 95 mgKOH / g or less and 80 mgKOH / g or less from the viewpoint of excellent compatibility with other components and good solvent resolubility. Even more preferably.
In the present invention, the amine value of the block copolymer (P1) before salt formation is equivalent to the amount of hydrochloric acid necessary to neutralize 1 g of the solid content of the block copolymer before salt formation. It represents the mass (mg) of potassium hydroxide and is a value measured by the method described in JIS K 7237.

The block copolymer (P1) before salt formation has a carboxy group, and the acid value of the block copolymer is preferably 18 mgKOH / g or less, and more preferably 16 mgKOH / g or less. . This is because deterioration of solvent re-solubility and development adhesion can be prevented.
Further, the block copolymer (P1) before salt formation has a carboxy group, and the acid value of the block copolymer (P1) is preferably 1 mgKOH / g or more, preferably 2 mgKOH / g or more. More preferably it is. This is because the effect of suppressing development residue is improved.
In addition, in this invention, the acid value of the block copolymer (P1) before salt formation is the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of solid content of the block copolymer. Is a value measured by the method described in JIS K 0070.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, and preferably 2000 to 15000 from the viewpoint of improving colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000-12000.
Here, the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC).
In the present invention, the weight average molecular weight Mw of the block copolymer is determined as a standard polystyrene conversion value 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. , 20650, 10850, 5460, 2930, 1300, 580 (Easy 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 macromonomer, salt-type block copolymer, and graft copolymer that are the raw materials for the block copolymer are also subjected to the above conditions.

  In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.

  The manufacturing method of the said block copolymer is not specifically limited. Although a block copolymer can be produced by a known method, it is preferable to produce it by a living polymerization method. This is because chain transfer and deactivation are unlikely to occur, a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include a living anionic polymerization method such as a living radical polymerization method and a group transfer polymerization method, and a living cation polymerization method. A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, a block copolymer can be produced by first producing the A block and polymerizing the structural units constituting the B block into the A block. In the above production method, the order of polymerization of the A block and the B block can be reversed. Also, the A block and the B block can be manufactured separately, and then the A block and the B block can be coupled.

[Salt-type block copolymer]
In the present invention, the block copolymer is selected from the group consisting of at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the general formulas (1) to (3). You may use the salt type block copolymer in which the 1 or more types of compound formed the salt.
The salt-type block copolymer is preferably used from the viewpoint that the color material adsorbability is further improved and the color material dispersibility is improved at the salt forming site in the structural unit represented by the general formula (I).

(One or more compounds selected from the group consisting of the general formulas (1) to (3))
In the general formulas (1) to (3), R ^a , R ^b , R ^{b ′} , R ^{b ″} , R ^c , R ^d , R ^e , and R ^f are linear or branched chains having 1 to 20 carbon atoms. Alternatively, the cyclic alkyl group may be linear or branched, and may contain a cyclic structure. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An undecyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a tetradecyl group, an octadecyl group, etc. are mentioned, Preferably a C1-C15 linear, branched or cyclic alkyl group is mentioned, More preferably, it is carbon number. 1-8 straight Examples include a chain, branched chain, or cyclic alkyl group.
In R ^a , R ^c , R ^d , and R ^e , examples of the substituent of the phenyl group or benzyl group which may have a substituent include an alkyl group having 1 to 5 carbon atoms and an acyl group. And an acyloxy group.

In R ^b , R ^{b ′} , R ^{b ″} , and R ^f , examples of the substituent of the phenyl group or benzyl group that may have a substituent include an acidic group or an ester group thereof, and those having 1 to 1 carbon atoms. 5 alkyl groups, acyl groups, acyloxy groups and the like.
In R ^b , R ^{b ′} , R ^{b ″} , and R ^f , as a substituent of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a vinyl group Includes an acidic group or an ester group thereof, a phenyl group, an acyl group, an acyloxy group, and the like.
In R ^b , R ^{b ′} , R ^{b ″} , and R ^f , the acidic group refers to a group that exhibits acidity by releasing protons in water. Specific examples of the acidic group include a carboxy group (—COOH), A sulfo group (—SO ₃ H), a phosphono group (—P (═O) (OH) ₂ ), a phosphinico group (> P (═O) (OH)), a boronic acid group (—B (OH) ₂ ), A borinic acid group (> BOH) and the like, and an anion having a hydrogen atom dissociated such as a carboxylate group (—COO ⁻ ), and a salt of an alkali metal ion such as sodium ion or potassium ion It may be an acid salt formed.
Moreover, as an ester group of an acidic group, carboxylic acid ester (—COOR), sulfonic acid ester (—SO ₃ R), phosphoric acid ester (—P (═O) (OR) ₂ ), (> P (═O ) (OR)), boronic acid ester (—B (OR) ₂ ), borinic acid ester (> BOR) and the like. Among them, the acidic ester group is preferably a carboxylic acid ester (—COOR) from the viewpoint of dispersibility and dispersion stability. R is a hydrocarbon group and is not particularly limited, but is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group or an ethyl group, from the viewpoint of dispersibility and dispersion stability. More preferred.

The compound of the general formula (2) includes a carboxy group, a boronic acid group, a borinic acid group, anions thereof, and alkali metal salts thereof from the viewpoints of dispersibility, dispersion stability, alkali developability, and development residue suppression. It is preferable to have one or more functional groups selected from these ester groups, and among them, it is more preferable to have a functional group selected from a carboxy group, a carboxylate group, a carboxylic acid group, and a carboxylic acid ester. It is particularly preferable to contain a carboxy group.
When the compound of the general formula (2) has an acidic group and an ester group thereof (hereinafter referred to as an acidic group or the like), both the acidic group equivalent side and the halogen atom side hydrocarbon of the compound have terminal nitrogen. Although it is possible to form a salt with the site, it is presumed that the terminal nitrogen site and the halogen atom-side hydrocarbon form a salt more stably than when the terminal nitrogen site and an acidic group form a salt. And it is estimated that a dispersibility and dispersion stability improve because a coloring material adsorb | sucks to the salt formation site | part which exists stably. Further, when the compound of the general formula (2) has an acidic group or the like, the dispersant is excellent in alkali developability. In particular, when the block copolymer (P1) has an acid value, that is, a structural unit derived from an acidic group-containing monomer such as a carboxy group is included in the solvophilic portion (B block) of the block copolymer (P1). In the case of having an acid value, if the acidic group or the like that increases the acid value is present at the salt forming site, the effect of suppressing development residue is enhanced. In addition, having an acidic group or the like that increases the acid value at a salt-forming site means that an acidic group that forms a salt by reacting with the terminal nitrogen site of the structural unit represented by the general formula (I) And having an acidic group that does not form a salt directly with the nitrogen moiety. For example, when the compound of the general formula (2) has an acidic group or the like, the compound of the general formula (2) is converted into a terminal nitrogen moiety and halogen atom side carbonization of the structural unit represented by the general formula (I). Since hydrogen forms a salt, the salt-forming site has an acidic group that does not form a salt, and the acid value is increased.

  When the compound of the general formula (2) has the acidic group or the like, it may have two or more acidic groups or the like. When two or more acidic groups or the like are included, the plurality of acidic groups or the like may be the same or different. The number of the acidic groups and the like that the compound of the general formula (2) has is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

R ^a in the general formula (1), at least one of R ^b , R ^{b ′} and R ^{b ″ in} the general formula (2), and at least one of R ^c and R ^d in the general formula (3) When one of them has an aromatic ring, the affinity with the skeleton of the coloring material described later is improved, the coloring material has excellent dispersibility and dispersion stability, and a colored composition having excellent contrast is obtained. It is preferable because it can be used.

  The molecular weight of the one or more compounds selected from the group consisting of the general formulas (1) to (3) is preferably 1000 or less, particularly 50 to 800, from the viewpoint of improving the colorant dispersibility. Is more preferable, it is preferable that it is 50-400, still more preferable is 80-350, and it is most preferable that it is 100-330.

Examples of the compound represented by the general formula (1) include benzene sulfonic acid, vinyl sulfonic acid, methane sulfonic acid, p-toluene sulfonic acid, monomethyl sulfuric acid, monoethyl sulfuric acid, mono n-propyl sulfuric acid and the like. A hydrate such as p-toluenesulfonic acid monohydrate may be used. Examples of the compound represented by the general formula (2) include 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, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethyl Examples include benzoic acid, 4-iodophenylbenzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3- (bromomethyl) phenylboronic acid, and the like. Examples of the compound represented by the general formula (3) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like. .
The group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutyl phosphoric acid, benzyl chloride, benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid monohydrate because of particularly excellent dispersion stability Preferably, one or more selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid monohydrate is used. Is preferred.
Further, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodo are excellent in dispersion stability and the effect of suppressing the development residue is improved by combination with the block copolymer (P1) having an acid value. One or more selected from the group consisting of phenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid are also preferably used.

In the salt-type block copolymer, the content of one or more compounds selected from the group consisting of the general formulas (1) to (3) is the terminal of the constituent unit represented by the general formula (I). Since it forms a salt with the nitrogen moiety, the group consisting of the above general formulas (1) to (3) with respect to 1 mol of the terminal nitrogen moiety of the structural unit represented by the general formula (I) One or more compounds selected from are preferably 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.2 mol or more, and 0.3 mol or more. It is particularly preferable that If it is at least the above lower limit value, the effect of improving the colorant dispersibility due to salt formation is likely to be obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When it is not more than the above upper limit value, it can be excellent in development adhesion and solvent re-solubility.
In addition, the 1 or more types of compound selected from the group which consists of said general formula (1)-(3) may be used individually by 1 type, and may combine 2 or more types. When combining 2 or more types, it is preferable that the total content is in the above range.

The salt type block copolymer is prepared by adding one or more compounds selected from the group consisting of the general formulas (1) to (3) in a solvent in which the block copolymer is dissolved or dispersed. And a method of heating, if necessary, and the like.
In addition, the terminal nitrogen part which the structural unit represented by the said general formula (I) of the block copolymer has, and one or more compounds selected from the group consisting of the above general formulas (1) to (3) The formation of a salt and the proportion thereof can be confirmed by a known method such as NMR.

The amine value of the obtained salt-type block copolymer has a value that is smaller by the amount of salt formation than the block copolymer before salt formation. However, since the salt formation site is the same as the terminal nitrogen site corresponding to the amino group, or rather becomes a strengthened color material adsorption site, the color material dispersibility and color material dispersion stability tend to be improved by salt formation. is there. In addition, like the amino group, if the salt forming site is too much, the solvent resolubility is adversely affected. Therefore, in the present invention, the amine value of the block copolymer (P1) before salt formation can be used as an index for improving colorant dispersion stability and solvent resolubility.
The amine value of the obtained salt-type block copolymer is preferably 0 to 110 mgKOH / g, and more preferably 0 to 100 mgKOH / g or less.
If it is below the above upper limit, the compatibility with other components is excellent, and the solvent resolubility becomes good.

In addition, the amine value of the salt type block copolymer salt-formed with the compound represented by the general formula (2) among the salt type block copolymer (P2) is determined by the method described in JIS K 7237. It can be a measured value. In the compound of the general formula (2), since the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the halogen atom side hydrocarbon form a salt, the salt is also formed by the measurement method. This is because the amine value can be measured without any change.
On the other hand, among the salt-type block copolymer (P2), the amine value of the salt-type block copolymer salt-formed by the compound represented by the general formula (1) or (3) is the salt described above. It calculates | requires by calculating as follows from the amine value of the block copolymer before formation. In the compound represented by the general formula (1) or (3), the terminal nitrogen site and the acidic group of the structural unit represented by the general formula (I) form a salt. This is because when the amine value of the copolymer is measured by the method described in JIS K 7237, the state of salt formation is changed and an accurate value cannot be measured.
First, the amine value of the block copolymer (P1) before salt formation is determined by the method described above. Next, using 13C-NMR, the group consisting of the general formula (1) or (3) with respect to the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the salt block copolymer The reaction rate of one or more compounds selected from (the ratio of the nitrogen moiety at the terminal of the salt formation) is measured. The terminal nitrogen moiety of the structural unit represented by the general formula (I) formed by salt formation of one or more compounds selected from the group consisting of the general formula (1) or (3) has an amine value of 0. As calculated, (amine value of block copolymer before salt formation (P1)) × (nitrogen site ratio (%) / 100 at the terminal of salt formation calculated from 13C-NMR spectrum) It can be determined by subtracting the amine value consumed by salt formation from the amine value of the block copolymer before salt formation.
Amine value of salt-type block copolymer (P2) = {amine value of block copolymer before salt formation (P1) measured by the method described in JIS K 7237}-{measured by the method described in JIS K 7237 Of the block copolymer before salt formation (P1) to be formed} × {nitrogen moiety ratio (%) / 100} at the terminal of salt formation calculated from 13C-NMR spectrum

Further, in the salt type block copolymer (P2), the acid value of the block copolymer (P1) before salt formation is 18 mgKOH / g or less, and the acid of the salt type block copolymer (P2). The value is preferably 55 mgKOH / g or less from the viewpoint of preventing deterioration of solvent resolubility and development adhesion.
Moreover, from the point which the inhibitory effect of a development residue improves, in the said salt type block copolymer (P2), the block copolymer (P1) before salt formation contains the structural unit derived from a carboxy group containing monomer. The acid value of the block copolymer (P1) is 1 mgKOH / g or more, and the acid value of the salt-type block copolymer (P2) after salt formation is the block copolymer (P1). The acid value is preferably larger than the acid value.
The acid value of the block copolymer (P1) in the salt-type block copolymer (P2) is particularly preferable in that the effect of suppressing the development residue is improved and the solvent resolubility and the development adhesion are improved. Is 1 to 18 mgKOH / g, the acid value of the salt-type block copolymer (P2) is preferably 1 to 55 mgKOH / g, and the acid value of the block copolymer (P1) is 1 to 18 mgKOH / g. It is more preferable that the salt block copolymer (P2) has an acid value of 2 to 55 mgKOH / g, and the block copolymer (P1) has an acid value of 2 to 16 mgKOH / g, The acid value of the salt-type block copolymer (P2) is more preferably 3 to 50 mgKOH / g.

In the salt type block copolymer (P2), when the acid value of the block copolymer (P1) before salt formation is 0 mgKOH / g, the salt type block copolymer (P2) has an acid value. However, the effect of suppressing development residue is hardly improved. On the other hand, when the acid value of the block copolymer (P1) before salt formation is 1 mgKOH / g or more, the acid value of the salt type block copolymer (P2) is the acid of the block copolymer (P1). When the value is larger than the value, the effect of suppressing the development residue is improved.
The acid value of the block copolymer (P1) is derived from a structural unit derived from an acidic group-containing monomer such as a carboxy group present in the B block which is a solvophilic site, and the acidic group is a solvophilic site. Because it is located very close to other components (alkali-soluble resin, polyfunctional monomer, etc.) and developer other than coloring materials, it is thought that the influence on development residue and solvent resolubility is great. . On the other hand, the acid value increased in the salt-type block copolymer (P2) is attributed to the acidic group bonded to the adsorbing site of the coloring material, so that the acidic group is separated from the other components. Therefore, the influence on the development residue and solvent re-solubility is considered to be small.
Moreover, when the acid value of the block copolymer (P1) before salt formation is 1 mgKOH / g or more, the acid value of the salt-type block copolymer (P2) after salt formation is the block copolymer (P1). When the acid value is larger than the acid value, the solvophilic portion and the coloring material adsorption portion have acidic groups, and the entire dispersant has a wide acid value. Under the situation where the solvophilic part has developability, the coloring material is easily absorbed while being adsorbed to the dissolving dispersant, and the coloring material is not left on the base material. Is estimated to improve.

As described above, the acid value of the block copolymer (P1) before salt formation is the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the block copolymer. And is a value measured by the method described in JIS K 0070.
Further, the acid value of the salt type block copolymer in which the salt type block copolymer (P2) is salt-formed with the compound represented by the general formula (2) is also measured by the method described in JIS K 0070. Is the value to be In the compound of the general formula (2), since the terminal nitrogen moiety of the structural unit represented by the general formula (I) and the halogen atom side hydrocarbon form a salt, the salt is also formed by the measurement method. This is because it can be measured without change.
On the other hand, when the salt type block copolymer (P2) is a salt type block copolymer that is salt-formed by the compound represented by the general formula (1) or (3), the salt type block copolymer (P2) is used for salt formation. The acid value is calculated by removing the acidic groups. This is because the acidic group used for salt formation does not function as an acidic group that increases the acid value of the dispersant. Therefore, in this application, the acid value of the salt type block copolymer salt-formed with the compound represented by the general formula (1) or (3) is calculated by a value obtained by the following formula. When the acid value of the salt-type block copolymer salt-formed by the compound represented by the general formula (1) or (3) is measured by the method described in JIS K 0070, it changes to a salt-forming state. This is because an accurate value cannot be measured.

Acid value of the salt-type block copolymer (P2) = {total acid value of the compound represented by the general formula (1) or (3) used for salt formation−acid value consumed by salt formation} + salt Acid value of block copolymer (P1) before formation Here, the total acid value of the compound represented by the general formula (1) or (3) used for the salt formation is described in JIS K 0070. It can be measured by the method. On the other hand, the acid value consumed by salt formation is calculated from the salt formation ratio obtained by NMR.
Specifically, the acid value consumed by salt formation is determined by, for example, measuring a 13C-NMR spectrum using a nuclear magnetic resonance apparatus, and in the obtained spectrum data, nitrogen that is not salt-formed at the terminal nitrogen site. From the ratio of the integrated value of the carbon atom peak adjacent to the atom and the carbon atom peak adjacent to the salt formed nitrogen atom, the ratio of the number of terminal nitrogen sites formed to the salt to the total number of terminal nitrogen sites is calculated. . (Amine number of the block copolymer before salt formation (P1) measured by the method described in JIS K 7237) × (the ratio of the nitrogen moiety at the terminal of the salt formation calculated from the 13C-NMR spectrum (%) / 100), the consumed amine value is calculated, and this value is the same as the acid value consumed by salt formation.
However, when 1 mol or less of the compound represented by the general formula (1) is salt-formed with respect to 1 mol of the terminal nitrogen moiety of the structural unit represented by the general formula (I), the acidic group is 1 When the salt of the compound represented by the general formula (3) having 1 mol or less is formed, or the compound represented by the general formula (3) having two acidic groups is salted by 0.5 mol or less. When forming, if the total amount of acidic groups forms a salt with the terminal nitrogen moiety of the structural unit represented by the general formula (I), in the salt-type block copolymer after the salt formation, the acidic group Since does not affect the acid value, it has the same acid value as the block copolymer before salt formation.
On the other hand, when the compound represented by the general formula (3) having two acidic groups is added in a mole number exceeding the above, there is an acidic group that is not salt-formed in the dispersant even after the salt is formed. Therefore, as shown in the above formula, the acid value of the acidic group that has not formed a salt is added to the acid value of the block copolymer before the salt formation to calculate the acid value of the dispersant.

Moreover, in this invention, the glass transition temperature of a dispersing agent is 30 degreeC or more. That is, regardless of whether the dispersant is the block copolymer (P1) or the salt type block copolymer (P2), the glass transition temperature thereof is 30 ° C. or higher.
When the glass transition temperature of the dispersant is less than 30 ° C., the development adhesiveness is lowered particularly when it is equal to or lower than the developer temperature (usually about 23 ° C.). This is presumed that when the glass transition temperature is equal to or lower than the developer temperature, the movement of the dispersant increases during development, resulting in deterioration in development adhesion.
The glass transition temperature of the dispersant is preferably 45 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoint of increasing the development adhesion and the effect of suppressing changes in color materials such as precipitation of aggregates. On the other hand, the temperature is preferably 200 ° C. or lower from the viewpoint of operability during use, such as easy precision weighing.
The glass transition temperature of the dispersant in the present invention is determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

However, the glass transition temperature (Tg) of the block copolymer not forming salt can be calculated by the following formula and used as an index.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the block copolymer. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. As the glass transition temperature value (Tgi) of the homopolymer of each monomer, the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
The glass transition temperature based on the calculated value is almost the same as the value measured by the DSC as shown in the examples described later, and can be used as an index of the glass transition temperature of the block copolymer that is not salt-formed. it can.

In the color material dispersion of the present invention, as the dispersant, at least one of the block copolymer and the salt type block copolymer is used, and the content thereof is the type of the color material to be used, and further for a color filter to be described later. It is suitably selected according to the solid content concentration in the photosensitive colored resin composition.
The content of the dispersant is from 3 to 45 parts by mass, more preferably from 5 to 35 parts by mass, with respect to 100 parts by mass of the total solid content in the colorant dispersion, from the viewpoint of dispersibility and dispersion stability. It is preferable to mix.
In particular, when forming a coating film or a colored layer having a high color material concentration, the content of the dispersant is 3 to 25 parts by mass, more preferably 100 parts by mass of the total solid content in the color material dispersion. It is preferable to mix | blend in the ratio of 5-20 mass parts.
In the present invention, the solid content is everything other than the solvent described above, and includes monomers dissolved in the solvent.

<Color material>
In the present invention, the color material is not particularly limited as long as it can form a desired color when the color layer of the color filter is formed. Or a mixture of two or more. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.

C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175;
C. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 06,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265;
C. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Pigment green 7, 36, 58;
C. I. Pigment brown 23, 25;
C. I. Pigment Black 1 and 7.

  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.

  For example, when forming a pattern of a light shielding layer on the color filter substrate as a photosensitive color resin composition for a color filter, which will be described later, the color material dispersion of the present invention, a black pigment having a high light shielding property is used in the ink. Blend. As the black pigment having a high light shielding property, for example, an inorganic pigment such as carbon black or iron trioxide or an organic pigment such as cyanine black can be used.

Examples of the dispersible dye include dyes that have been made dispersible by imparting various substituents to the dye, or insolubilized in a solvent using a known rake (chlorination) technique, and solvents having low solubility The dye which became dispersible by using in combination is mentioned. By using such a dispersible dye in combination with the dispersant, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
As a guide, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

In the present invention, the colorant preferably contains one or more selected from the group consisting of phthalocyanine pigments, diketopyrrolopyrrole pigments, and quinophthalone pigments.
In the case where the coloring material contains a phthalocyanine pigment, it is preferable from the viewpoint that it interacts with the specific dispersant to improve luminance and heat resistance. In the case where the coloring material contains one or more selected from the group consisting of diketopyrrolopyrrole pigments and quinophthalone pigments, which are likely to precipitate the pigment aggregates through a high-temperature heating step after fine dispersion. It is preferable from the viewpoint that the precipitation of the pigment aggregates is suppressed even when a high temperature heating step is performed after fine dispersion by interacting with the specific dispersant.
In the case of a normal dispersant, the color material is easily desorbed by heating and the color material surface is exposed, so that the specific dispersant used in the present invention has a strong adsorptive power to the color material. Therefore, there is little detachment | desorption of a dispersing agent at the time of a heating. Therefore, pigment aggregates are precipitated like pigments such as phthalocyanine pigments whose crystallinity is easily changed by heating, or whose color changes and brightness is easily lowered, diketopyrrolopyrrole pigments, and quinophthalone pigments. Even if it is an easy pigment, the above changes can be suppressed by maintaining adsorption of the dispersant during heating.

The average primary particle size of the color material used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a color layer of a color filter, and varies depending on the type of color material used. Is preferably in the range of 10 to 100 nm, more preferably 15 to 60 nm. When the average primary particle diameter of the color material is in the above range, a display device including a color filter manufactured using the color material dispersion of the present invention can be made with high contrast and high quality. .
The average primary particle size of the color material in the present invention can be determined by taking an enlarged photograph with a transmission electron microscope or a scanning electron microscope and calculating the “volume distribution median diameter (D50)” by a known method. . Specifically, by attaching a special bright field STEM sample stage and an optional detector to a field emission scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, a scanning transmission electron microscope (hereinafter, “ Abbreviated as "STEM"), take a 200,000 times STEM photo, import it into the following software, select 100 color materials on the photo, and measure the diameter (passing length) of each. From the volume-based distribution, the 50% cumulative particle size is obtained by volume.
A measurement sample to be subjected to STEM is prepared by mixing a coloring material and toluene and dropping the mixture onto a collodion film-attached mesh. Further, when obtaining a volume-based particle size distribution or volume distribution median diameter (D50) from the STEM photograph, image analysis type particle size distribution measurement software “Mac-View Ver. 4” manufactured by Mountec Co., Ltd. is used.

Moreover, although the average dispersed particle diameter of the color material in the color material dispersion varies depending on the type of the color material used, it is preferably within the range of 10 to 100 nm, and more preferably within the range of 15 to 60 nm. preferable.
The average dispersed particle size of the color material in the color material dispersion is the dispersed particle size of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. For particle size measurement with a laser light scattering particle size distribution meter, the color material dispersion is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is a volume average particle size.

  The coloring material used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Further, a commercially available color material may be used after being refined.

In the color material dispersion of the present invention, the content of the color material is not particularly limited. The content of the color material is 5 to 80 parts by mass, more preferably 8 to 70 parts by mass with respect to 100 parts by mass of the total solid content in the color material dispersion from the viewpoint of dispersibility and dispersion stability. It is preferable to mix.
When forming a coating or colored layer having a particularly high colorant concentration, the ratio of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, relative to 100 parts by mass of the total solid content in the colorant dispersion. It is preferable to mix with.

[solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the colorant dispersion and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Tone solvents; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate and butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene Glycol ether solvents such as glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; γ-butyrolactone, etc. Lactone solvents; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; Examples thereof include organic solvents such as aromatic hydrocarbons such as xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, And it is 1 or more types selected from the group which consists of 3-methoxybutyl acetate from the point of the solubility of another component, and the applicability | paintability.

  In the color material dispersion of the present invention, the solvent as described above is usually preferably in the range of 55 to 95% by mass, particularly 65 to 90% by mass with respect to the total amount of the color material dispersion containing the solvent. % Is preferably within the range of 70% to 88% by mass. When there is too little solvent, a viscosity will rise and a dispersibility will fall easily. Moreover, when there are too many solvents, color material density | concentration will fall and it may be difficult to achieve to a target chromaticity coordinate.

(Other ingredients)
As long as the effect of this invention is not impaired, you may mix | blend a dispersion auxiliary resin and another component with the coloring material dispersion liquid of this invention as needed.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by a photosensitive color resin composition for a color filter described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant 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.

  The color material dispersion of the present invention is used as a preliminary preparation for preparing a photosensitive colored resin composition for a color filter described later. That is, the color material dispersion is preliminarily prepared in the previous stage of preparing a photosensitive colored resin composition for a color filter described later, (color material component mass in the composition) / (color material component in the composition). Is a colorant dispersion having a high solid content mass ratio. Specifically, the ratio of (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the colorant dispersion and each component described later, a photosensitive colored resin composition for a color filter having excellent dispersibility can be prepared.

[Production method of colorant dispersion]
In the present invention, a method for producing a color material dispersion is a method in which a color material dispersion in which the color material is dispersed in a solvent by a dispersant of the block copolymer or the salt type block copolymer is obtained. If there is no particular limitation. Especially, it is preferable to set it as either of the following two manufacturing methods from the point which is excellent in the dispersibility and dispersion stability of a coloring material.

  That is, a first method for producing a colorant dispersion according to the present invention includes a step of preparing a dispersant for the block copolymer or a salt-type block copolymer, and in the presence of the dispersant in a solvent. And a step of dispersing the color material.

  In addition, the second production method of the colorant dispersion according to the present invention in the case of using a dispersant that is a salt type block copolymer includes a solvent, the block copolymer, and the general formulas (1) to ( 3) One or more compounds selected from the group consisting of 3) and a coloring material are mixed, and at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) is combined with the compound. And a step of dispersing the coloring material while forming a salt.

In the case of using the salt type block copolymer, according to the first production method, after preparing the salt type block copolymer, the color material is dispersed using the salt type block copolymer as a dispersant. Therefore, from the point which can confirm the reaction end point and reaction rate of the block copolymer before salt formation, and the 1 or more types of compound selected from the group which consists of said general formula (1)-(3) correctly. preferable.
Further, according to the second production method, the color material is dispersed without preparing the salt type block copolymer by self-aggregation because the color material is dispersed while preparing the dispersant for the salt type block copolymer. A liquid can be prepared efficiently and dispersibility can be improved.

In the first production method and the second production method, the color material can be dispersed using a conventionally known disperser.
Specific examples of the dispersing machine include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous 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 3.0 mm, and more preferably 0.05 to 2.0 mm.

  Specifically, preliminary dispersion is performed with 2.0 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a 0.5-2 micrometer filter after dispersion | distribution.

[Photosensitive colored resin composition for color filter]
The photosensitive colored resin composition for a color filter according to the present invention contains the color material dispersion according to the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.
The photosensitive colored resin composition for a color filter of the present invention is excellent in color material dispersion stability by using the color material dispersion according to the present invention, and development adhesion is suppressed while the generation of development residue is suppressed. A colored layer having excellent re-solubility and excellent contrast can be formed.

  The photosensitive colored resin composition for a color filter of the present invention contains at least a colorant, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. Other components may be contained as long as the effects are not impaired. Hereinafter, although each component contained in the photosensitive colored resin composition for a color filter of the present invention will be described, the dispersant, the color material, and the solvent are the same as those described in the color material dispersion of the present invention. Since there is, explanation here is omitted.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and is suitably selected from developers used for pattern formation, particularly preferably those that are soluble in an alkali developer. Can be used.
A preferable alkali-soluble resin in the present invention is a resin having a carboxy group as an acidic group, and specific examples thereof include an acrylic copolymer having a carboxy group and an epoxy (meth) acrylate resin having a carboxy group. Among these, particularly preferred are those having a carboxy 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 carboxy group is obtained by copolymerizing a carboxy group-containing ethylenically unsaturated monomer and another ethylenically unsaturated monomer.

Specific examples of the acrylic copolymer having a carboxy group include those described in JP2013-029832A, and specifically include, for example, methyl (meth) acrylate, ethyl (meta ) A copolymer composed of a monomer having no carboxy group such as acrylate, and one or more selected from (meth) acrylic acid and anhydrides thereof. 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, the addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is particularly preferable in that the sensitivity and film strength of the colored layer become more stable.

  The copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer in the carboxy group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, when the copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, if the copolymerization ratio exceeds 50% by mass, there is a tendency that pattern chipping or film roughness on the pattern surface tends to occur during development with an alkali developer.

The weight average molecular weight (Mw) of the carboxy group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be remarkably lowered. If it exceeds 50,000, pattern formation may be difficult during development with an alkali developer.
In addition, the said weight average molecular weight (Mw) of a carboxy-group containing copolymer can be measured by Shodex GPC system-21H (polystyrene) as a standard substance and THF as an eluent (Shodex GPC System-21H).

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxy group, Epoxy (meth) obtained by making the reaction product of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones. The epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.

  The alkali-soluble resin used in the photosensitive colored resin composition for color filters may be used singly or in combination of two or more, and the content is not particularly limited. The alkali-soluble resin is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass, based on the total solid content of the photosensitive colored resin composition for a filter. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is more than the above upper limit, the film may be rough during development. Pattern chipping may occur. In the present invention, the solid content is everything except the above-mentioned solvent, and includes a liquid polyfunctional monomer.

<Multifunctional monomer>
The polyfunctional monomer used in the photosensitive colored resin composition for a color filter is not particularly limited as long as it can be polymerized by a photoinitiator described later, and usually has two or more ethylenically unsaturated double bonds. In particular, a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
Such a polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include those described in JP2013-029832A.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. When the photosensitive colored resin composition for color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Preferred are poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. (Meth) acrylate, succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) ) Succinic acid modified product of acrylate, dipen Hexa (meth) acrylate are preferable.
Although there is no restriction | limiting in particular in content of the said polyfunctional monomer used in the photosensitive coloring resin composition for color filters, Preferably a polyfunctional monomer is 5 with respect to solid content whole quantity of the photosensitive coloring resin composition for color filters. -60 mass%, More preferably, it exists in the range of 10-40 mass%. If the polyfunctional monomer content is less than the above lower limit, photocuring will not proceed sufficiently, and the exposed part may be eluted during development, and if the polyfunctional monomer content is greater than the above upper limit, alkali developability May decrease.

<Photoinitiator>
There is no restriction | limiting in particular as a photoinitiator used in the photosensitive coloring resin composition for color filters, It can use 1 type (s) or 2 or more types in combination from the conventionally well-known various photoinitiators. Specific examples thereof include those described in JP2013-029832A.
As a photoinitiator, although only 1 type may be used, you may use 2 or more types of compounds together. Among them, the photoinitiator preferably contains an oxime ester from the viewpoint of high effect of suppressing pattern chipping and water stain generation. As the oxime ester, those having an aromatic ring are preferable, and those having a condensed ring including an aromatic ring are preferable from the viewpoint of reducing the contamination of the photosensitive colored resin composition for color filters and the contamination of the apparatus by decomposition products. More preferably, it has a condensed ring including a benzene ring and a hetero ring.
Examples of oxime esters include 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H. -Carbazol-3-yl]-, 1- (o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, JP 2010-527339, JP 2010-527338, JP 2013-2013. The oxime ester photopolymerization initiator described in 041153 and the like can be appropriately selected. As commercially available products, Irgacure OXE-01, Irgacure OXE-02 (manufactured by BASF), ADEKA OPT-N-1919 (manufactured by Asahi Denka) and the like may be used.

  Moreover, it is preferable from the point of a sensitivity improvement to use the oxime ester in combination with the photoinitiator which has a tertiary amine structure. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure that is an oxygen quencher in the molecule, radicals generated from the initiator are hardly deactivated by oxygen, and sensitivity can be improved. is there. As a commercial item of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone (for example, High Cure ABP, Kawaguchi Pharmaceutical).

  The content of the photoinitiator used in the photosensitive colored resin composition for color filters is not particularly limited, but the photoinitiator is preferably 3 to the total solid content of the photosensitive colored resin composition for color filters. It is 40 mass%, More preferably, it exists in the range of 10-30 mass%. If this content is less than the above lower limit, the photocuring will not proceed sufficiently, and the exposed part may be eluted during development, while if it exceeds the above upper limit, the yellowing of the resulting colored layer will become strong and the luminance will be high. May decrease.

<Optional components>
The photosensitive colored resin composition for color filters may contain various additives as necessary.
Examples of the additive include an antioxidant, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter. Can be mentioned.

  The photosensitive colored resin composition for color filters of the present invention preferably further contains an antioxidant from the viewpoint of heat resistance. The antioxidant may be appropriately selected from conventionally known antioxidants. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. From the viewpoint, it is preferable to use a hindered phenol-based antioxidant.

  When using antioxidant, the compounding quantity will not be specifically limited if it is a range by which the effect of this invention is not impaired. As a compounding quantity of antioxidant, it is preferable that antioxidant is 0.1-5.0 mass% with respect to the solid content whole quantity in the photosensitive coloring resin composition for color filters, 0.5- It is more preferable that it is 4.0 mass%. If it is more than the said lower limit, it is excellent in heat resistance. On the other hand, if it is below the said upper limit, the photosensitive colored resin composition for color filters of this invention can be used as the highly sensitive photosensitive colored resin composition for color filters.

  Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

<Combination ratio of each component in photosensitive colored resin composition for color filter>
The total content of the color materials is preferably blended in a proportion of 3 to 65 mass%, more preferably 4 to 60 mass%, based on the total solid content of the photosensitive colored resin composition for color filters. If it is more than the said lower limit, the colored layer at the time of apply | coating the photosensitive coloring resin composition for color filters to predetermined | prescribed film thickness (usually 1.0-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. When forming a colored layer having a particularly high color material concentration, the content of the color material is from 15 to 65% by mass, more preferably from 25 to 65% by mass, based on the total solid content of the photosensitive colored resin composition for color filters. It is preferable to mix | blend in the ratio of 60 mass%.
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the content of the dispersant is based on the total solid content of the photosensitive colored resin composition for color filters. 1 to 40% by mass can be used. Furthermore, it is preferable to mix | blend in the ratio of 2-30 mass% with respect to the solid content whole quantity of the photosensitive coloring resin composition for color filters, and it is preferable to mix | blend especially in the ratio of 3-25 mass%. If it is more than the said lower limit, it is excellent in the storage stability of the dispersibility and dispersion stability of a color material, and the photosensitive coloring resin composition for color filters. Moreover, if it is below the said upper limit, the intensity | strength of a colored layer will be excellent.
When a colored layer having a particularly high colorant concentration is formed, the content of the dispersant is 2 to 25% by mass, more preferably 3 to the total solid content of the photosensitive colored resin composition for color filters. It is preferable to mix | blend in the ratio of 20 mass%. In the case of a salt block copolymer, the mass of the dispersant is one or more compounds selected from the group consisting of the block copolymer before salt formation and the above general formulas (1) to (3). And the total mass.
Moreover, what is necessary is just to set content of a solvent suitably in the range which can form a colored layer accurately. The total amount of the photosensitive colored resin composition for color filters containing the solvent is usually preferably in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass. preferable. When the content of the solvent is within the above range, the coating property can be excellent.

<Method for Producing Photosensitive Colored Resin Composition for Color Filter>
The method for producing the photosensitive colored resin composition for color filters of the present invention is not particularly limited. For example, the colorant dispersion of the present invention includes an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and the necessity. Accordingly, other components can be added and mixed using a known mixing means.

[Color filter]
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 is the color filter photosensitivity according to the present invention. It has a colored layer formed by curing a colored resin composition.

  Such a color filter according to 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)
At least one colored layer used in the color filter of the present invention is a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the present invention.
The colored layer is usually formed in an opening of a light shielding part on a transparent substrate, which will be described later, and is usually 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 photosensitive 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 by the following method, for example.
First, the above-described photosensitive colored resin composition for a color filter of the present invention is transparently described later using coating means such as spray coating, dip coating, bar coating, roll coating, spin coating, and die coating. Apply onto the substrate to form a wet coating. Of these, spin coating and die coating can be preferably used.
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 cured by photopolymerizing an alkali-soluble resin and a polyfunctional monomer. Let it be a coating film. 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 photosensitive colored resin composition for 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 photosensitive colored resin composition for color filter 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 part is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like. Alternatively, the light shielding part may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, etc. is there.

  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 is set to about 0.5 to 2 μm in the case where a black pigment is dispersed or dissolved in a binder resin. Is done.

(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. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
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 is one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, and the like are formed in addition to the transparent substrate, the light shielding portion, and the colored layer. May be.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the color filter according to 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. Then, the color filter and the counter substrate are overlapped with each other under reduced pressure, and are adhered through a sealant, whereby a liquid crystal layer can be formed. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[Organic light emitting display]
An organic light emitting display device according to the present invention includes the above-described color filter according to 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.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
The amine value of the block copolymer before salt formation and the amine value of the salt-type block copolymer salt-formed with the compound represented by the general formula (2) are in accordance with the method described in JIS K 7237. Determined by the method.
The glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation is measured by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology) according to the method described in JIS K7121. It measured using.
The acid value of the block copolymer before salt formation and the acid value of the salt type block copolymer salt-formed with the compound represented by the general formula (2) are the methods described in JIS K 0070. It calculated | required by the method according to.
The weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.

Moreover, it calculated | required by calculating with a following formula about the glass transition temperature (Tg) of the block copolymer before salt formation.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the block copolymer. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature (Tgi) of each monomer was the value of Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)). Specifically, the homopolymer glass transition temperature values (Tgi) of the monomers used in the examples and comparative examples are as follows.
2-hydroxyethyl methacrylate (HEMA): 55 ° C.
2-ethylhexyl methacrylate (EHMA): -10 ° C
N-butyl methacrylate (BMA): 20 ° C.
Benzyl methacrylate (BzMA): 54 ° C
Methyl methacrylate (MMA): 105 ° C
Methacrylic acid (MAA): 185 ° C
Dimethylaminoethyl methacrylate (DMMA): 18 ° C
Dimethylaminopropyl methacrylamide (DMAPMA): 96 ° C
Dimethylaminopropyl acrylamide (DMAPAA): 134 ° C
2-hydroxy-3-phenoxypropyl acrylate (HPhPA) (trade name: M-600A, Kyoeisha Chemical Co., Ltd.): 17 ° C.
Methoxypolyethylene glycol (45) methacrylate (M-450G) (trade name: NK ester M-450G, Shin-Nakamura Chemical Co., Ltd.)
With respect to the block copolymers A-2 and A-3 of the following synthesis examples and the block copolymer A-16 of the comparative example, the glass transition temperature was calculated by the above method. About 2, 67 degreeC (DSC measured value 69 degreeC) about block copolymer A-3, 65 degreeC (DSC measured value 66 degreeC), about block copolymer A-16, 23 degreeC (DSC measured value) 23 ° C.), which is almost the same as the DSC measurement value.

(Synthesis Example 1: Production of block copolymer A-1)
In a 500 mL round bottom four-necked separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer and digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and initiator dimethylketenemethyltrimethylsilylacetal 5.81 Part by mass was added through an addition funnel, and nitrogen substitution was sufficiently performed. 0.5 parts by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of HEMA monomers for B block, 7.5 parts by mass of EHMA, 12.9 parts of BMA Part by mass, 10.7 parts by mass of BzMA, and 30.9 parts by mass of MMA were added dropwise using an addition funnel over 60 minutes. The temperature was kept below 40 ° C. by cooling the reaction flask with an ice bath. After 1 hour, 18.3 parts by mass of DMAPMA, which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and the A block containing the structural unit represented by the general formula (I) and the B block having solvophilicity, A block copolymer A-1 (amine value 60 mgKOH / g, Tg 64 ° C.) was obtained. The weight average molecular weight Mw was 7600.

(Synthesis Examples 2 to 5: Synthesis of block copolymers A-2 to A-5)
Block copolymers A-2 to A-5 were synthesized in the same manner as in Synthesis Example 1 except that the content was changed to the content shown in Table 1 in Synthesis Example 1. Table 1 shows the amine value, Tg, and acid value of the obtained block copolymer.

(Synthesis Example 6: Production of block copolymer A-6)
Add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine and 1.0 part by mass of methyl isobutyrate were injected using a syringe. B block monomer 1-ethoxyethyl methacrylate (EEMA) 0.4 parts by mass, HEMA 19.7 parts by mass, EHMA 7.5 parts by mass, BMA 12.9 parts by mass, BzMA 10.7 parts by mass, MMA 30.7 parts by mass The solution was added dropwise using an addition funnel over 60 minutes. After 30 minutes, 18.3 parts by mass of DMAPMA, which is a monomer for A block, which is a monomer for A block, was dropped over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, diluted with PGMEA to obtain a solid content solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the mixture was allowed to react for 7 hours. The structural unit derived from EEMA was deprotected to obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from a block containing a structural unit represented by the general formula (I) and a carboxy group-containing monomer A block copolymer A-6 (amine value 60 mgKOH / g, Tg 64 ° C., acid value 1 mgKOH / g) containing a B block having solvophilicity and a solvent. The weight average molecular weight Mw was 7000.

(Synthesis Example 7: Synthesis of block copolymer A-7)
A block copolymer A-7 was synthesized in the same manner as in Synthesis Example 6 except that the content was changed to the content shown in Table 1 in Synthesis Example 6. Table 1 shows the acid value, Tg, and amine value of the obtained block copolymer.
In Synthesis Example 7, 5.0 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. Table 1 shows the amine value, Tg, and acid value of the block copolymer.

(Synthesis Examples 8 to 18: Synthesis of block copolymers A-8 to A-18)
Block copolymers A-8 to A-18 were synthesized in the same manner as in Synthesis Example 1 except that the content in Synthesis Example 1 was changed to the content shown in Table 1. Table 1 shows the acid value, Tg, and amine value of the obtained block copolymer.

(Synthesis Example 19: Synthesis of Graft Copolymer A-19)
(1) Preparation of macromonomer 160.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was charged into a reactor equipped with a condenser, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and nitrogen. While stirring under an air stream, the temperature was raised to 90 ° C. HEMA 39.4 parts by mass, EHMA 15.0 parts by mass, BMA 25.8 parts by mass, BzMA 21.4 parts by mass, MMA 61.8 parts by mass, 2-mercaptoethanol 8.0 parts by mass, PGMEA 60 parts by mass, α, α'-azo A mixed solution of 2.0 parts by mass of bisisobutyronitrile (abbreviated as AIBN) was added dropwise over 1.5 hours, and the reaction was further continued for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., 17.48 parts by weight of Karenz MOI (manufactured by Showa Denko KK), 0.25 parts by weight of dibutyltin dilaurate, p-methoxyphenol The macromonomer solution was obtained by adding 0.25 mass part and 20 mass parts of PGMEA, and stirring for 3 hours. The obtained macromonomer solution was reprecipitated in hexane, purified by filtration and vacuum drying, and macromonomer A was obtained. The obtained macromonomer A had a weight average molecular weight Mw of 4000.
(2) Preparation of graft copolymer A reactor equipped with a cooling pipe, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by mass of PGMEA, and the temperature was maintained while stirring under a nitrogen stream. Warmed to 85 ° C. A mixed solution of 87.8 parts by mass of Macromonomer A prepared in (1), 18.3 parts by mass of DMAPMA, 1.24 parts by mass of n-dodecyl mercaptan, 20.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN was 1.5. After dripping over time and heating and stirring for 3 hours, a mixed solution of AIBN 0.10 parts by mass and PGMEA 10.0 parts by mass is added dropwise over 10 minutes, and further aged at the same temperature for 1 hour, thereby graft copolymer A-19 solution was obtained. Macromonomer A is a mass ratio (19.7: 7.5: 12.9: 10) of HEMA: EHMA: BMA: BzMA: MMA similar to block copolymer A-1 to 18.3 parts by mass of DMAPMA. .7: 30.9 (parts by mass)).
The obtained graft copolymer A-19 solution was reprecipitated in hexane, and purified by filtration and vacuum drying. The obtained graft copolymer A-19 had an amine value of 60 mgKOH / g, Tg of 64 ° C., and a weight average molecular weight Mw of 12000.

(Synthesis Example 20: Synthesis of Graft Copolymer A-20)
(1) Preparation of Macromonomer In Synthesis Example 19, 39.4 parts by mass of HEMA, 36.8 parts by mass, 14.0 parts by mass of EHMA, 14.0 parts by mass, and 25.8 BMA for the monomer ratio when preparing the macromonomer In the same manner as Macromonomer A, except that the mass part was changed to 24.0 parts by mass, BzMA 21.4 parts by mass to 20.0 parts by mass, and MMA 61.8 parts by mass to 38.4 parts by mass. Monomer B was prepared. The resulting macromonomer B had a weight average molecular weight Mw of 4100.
(2) Preparation of graft copolymer In Synthesis Example 19, the ratio of the macromonomer and DMAPMA when preparing the graft copolymer was changed to 71.6 parts by mass for macromonomer B and 33.4 parts by mass for DMAPMA. A graft copolymer A-20 was synthesized in the same manner as in Synthesis Example 19 except that. In addition, macromonomer B is the same mass ratio of HEMA: EHMA: BMA: BzMA: MMA as that of block copolymer A-3 (18.4: 7.0: 12.0) with respect to 33.4 parts by mass of DMAPMA. : 10.0: 19.2 (parts by mass)). Table 1 shows the amine value, Tg, weight average molecular weight Mw, and acid value of the obtained graft copolymer.

(Synthesis Example 21: Synthesis of salt type block copolymer A-21)
First, in the same manner as in Synthesis Example 1, a block copolymer A-1 (the block copolymer before salt formation of the salt type block copolymer A-21 and the block copolymer A-1 are the same) is synthesized. did.
10.0 parts by mass of block copolymer A-1 is dissolved in 40.6 parts by mass of PGMEA in a 100 mL round bottom flask, and phenylphosphinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a compound represented by the general formula (3). Add 0.15 parts by mass (the compound represented by the general formula (3) is 0.10 mol per 1 mol of the DMAPMA unit of the block copolymer A-1) and stir at a reaction temperature of 30 ° C. for 20 hours. As a result, a salt type block copolymer A-21 solution having a solid content of 20% by mass was obtained.
Since phenylphosphinic acid is a monovalent acid and the acidic group is used for salt formation, the acid value of the block copolymer after salt formation is the same as that of block copolymer A-1, but salt formation Specifically, the subsequent amine value was calculated as follows.
1 g of a mixed solution of 9 parts by mass of salt-type block copolymer A-21 (solid matter after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was put into an NMR sample tube, and the 13C-NMR spectrum was measured by nuclear magnetic resonance. Using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was performed under conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of amino groups that are salt-formed to the total number of amino groups is calculated, and is not different from the theoretical salt-forming ratio (the total phenylphosphinic acid and the nitrogen site at the end of DMAPMA of the block copolymer A-1) Salt formation).
The amine value after salt formation was calculated as 54 mgKOH / g by subtracting the amine value (6 mgKOH / g) of 0.10 mol of DMAPMA unit from the amine value before salt formation of 60 mgKOH / g. The Tg measurement result of the salt type block copolymer was 65 ° C.

(Synthesis Examples 22 to 29: Synthesis of salt type block copolymers A-22 to A-29)
In Synthesis Example 21, a salt-type block copolymer A-22 to A-29 solution was obtained in the same manner as in Synthesis Example 21 except that the salt-forming compounds were changed to the compounds and amounts shown in Table 2 (salts) The block copolymer A-2 to 29 before the salt formation and the block copolymer A-1 are the same).
Table 2 shows the amine value, acid value, and amine value, acid value, and Tg of the block copolymer before salt formation in the salt block copolymers A-22 to A-29.
In Table 2, the amount of one or more compounds selected from the group consisting of the compounds represented by the general formulas (1) to (3) is included in the structural unit represented by the general formula (I). Expressed in moles of the compound per mole of terminal nitrogen moiety (DMAPMA).

Further, since phenylphosphonic acid is a divalent acid, the amine value and acid value of the salt-type block copolymer A-26 were specifically calculated as follows.
First, in the same manner as in Synthesis Example 1, a block copolymer A-1 (the block copolymer before salt formation of the salt-type block copolymer A-26 and the block copolymer A-1 is the same) is synthesized. did.
In a 100 mL round bottom flask, 10.0 parts by mass of block copolymer A-1 is dissolved in 45.4 parts by mass of PGMEA, and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a compound represented by the general formula (3). 1.35 parts by mass (the compound represented by the general formula (3) is 0.80 mol with respect to 1 mol of the DMAPMA unit of the block copolymer A-1) and stirred at a reaction temperature of 30 ° C. for 20 hours. As a result, a salt type block copolymer A-26 solution having a solid content of 20% by mass was obtained.
Since phenylphosphonic acid is a divalent acid and the acidic group is present more than that used for salt formation, the acid value of the block copolymer after salt formation is higher than that of the block copolymer A-1. Specifically, the amine value after salt formation was calculated as follows.
1 g of a mixed solution of 9 parts by mass of salt-type block copolymer A-26 (solid after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was put into an NMR sample tube, and the 13C-NMR spectrum was measured by nuclear magnetic resonance. Using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was performed under conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of amino groups salted to the total number of amino groups was calculated, and it was confirmed that all amino groups were salted.
Since there was no amino group of DMAPMA that did not form a salt, the amine value after salt formation was calculated to be 0 mgKOH / g.
Since all of the amino groups of DMAPMA in the block copolymer A-1 are salted with phenylphosphonic acid, 62.5% of the phenylphosphonic acid out of the total phenylphosphonic acid is one molecule of the amino group of DMAPMA. The remaining 37.5% phenylphosphonic acid is salted with one amino group of DMAPMA in one molecule, and one of the two acidic groups is free (as acid value). Calculated state). The acid value of the block copolymer before salt formation is 0 mg KOH / g, the acid value measured by the method described in JIS K 0070 of phenylphosphonic acid is 96 mg KOH / g, and the amine value consumed by salt formation is Since it was 60 mgKOH / g, the acid value after salt formation was calculated as 0 + 96−60 = 36 mgKOH / g. In addition, the measurement result of Tg of the salt type block copolymer was 76 ° C.

(Synthesis Examples 30 to 31: Synthesis of salt type block copolymers A-30 to A-31)
First, the block copolymer A-7 was synthesized in the same manner as in Synthesis Example 7 (the block copolymer A-30 to 31 of the salt-type block copolymer A-30 to 31 and the block copolymer A-7). Are the same).
In Synthesis Example 21, except that the block copolymer A-1 was changed to the block copolymer A-7 and the salt-forming compound was changed to the compounds and amounts shown in Table 2, the same as in Synthesis Example 21, A salt type block copolymer A-30 to A-31 solution was obtained.
In addition, since the amine value and acid value of the salt type block copolymer A-31 using α-bromophenylacetic acid form a salt with a halogen atom, the amine value and acid of the block copolymer before salt formation are used. It was obtained by measuring in the same manner as the value.
Table 2 shows the amine value, acid value, and amine value, acid value, and Tg of the block copolymer before salt formation in the salt block copolymers A-30 to A-31.

(Synthesis Example 32: Synthesis of Salt Random Copolymer A-32)
A (3- (N, N-dimethylamino) propylacrylamide / methoxypolyethylene glycol (45) methacrylate copolymer described in Production Example 1 of Patent Document 1 (International Publication No. 2014/10687) is disclosed in Patent Document 1 (International The synthesis was conducted with reference to the description of Production Example 1 of Publication No. 2014/10687) to obtain a salt-type random copolymer A-32 solution, specifically, prepared as follows.
In a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer and digital thermometer, 45 parts by mass of PGMEA, 7.0 parts by mass of DMAPAA, 23 parts of M-450G 0.0 part by mass and 0.09 part by mass of 2-mercaptoethanol were added via an addition funnel, followed by sufficient nitrogen substitution. After raising the temperature to 78 ° C. in a nitrogen atmosphere, DMAPAA 16.3 parts by mass, M-450G 55.0 parts by mass, 2-mercaptoethanol 0.21 parts by mass, PGMEA 105.0 parts by mass, initiator 2 , 2-azobis- (2,4-dimethylvaleronitrile) was continuously added dropwise over 3 hours over 3 hours. After the dropwise addition, a solution prepared by dissolving 0.25 parts by mass of 2,2-azobis- (2,4-dimethylvaleronitrile) in 2.5 parts by mass of PGMEA was added, and the reaction was continued for 1 hour while maintaining 78 ° C. Further, a solution in which 0.25 part by mass of 2,2-azobis- (2,4-dimethylvaleronitrile) was dissolved in 2.5 parts by mass of PGMEA was added, and the reaction was continued for 1 hour while maintaining 78 ° C. (Amine value 83 mgKOH / g) was obtained. The weight average molecular weight Mw was 17900. After putting 150.0 parts by mass of the obtained copolymer solution into another 500 mL round bottom four-neck separable flask, nitrogen substitution was performed. Further, a solution in which 2.95 parts by mass of dimethylsulfuric acid was dissolved in 30.0 parts by mass of PGMEA (the number of moles of dimethylsulfuric acid relative to 1 mol at the nitrogen part at the end of DMAPAA was 0.27) was dropped at 85 ° C. in a nitrogen atmosphere. The reaction was performed for 3 hours. The obtained salt-type copolymer solution was reprecipitated in hexane, purified by filtration and vacuum drying, and salt-type random copolymer A-32 (Tg-23 ° C.) was obtained.

(Synthesis Examples 33 to 36: Synthesis of salt type block copolymers A-33 to A-36)
First, in the same manner as in Synthesis Example 17, a block copolymer A-17 was synthesized.
Instead of the block copolymer A-1 in Synthesis Example 21, the block copolymer A-17 (the block copolymer before salt formation of the salt-type block copolymer A-33 and the block copolymer A-1) A salt type block copolymer A-33 to A-36 solution was obtained in the same manner as in Synthesis Example 21 except that -17 was the same.
Table 2 shows the amine value, acid value, and amine value, acid value, and Tg of the block copolymer before salt formation in the salt type block copolymers A-33 to A-36.

(Synthesis Examples 37 to 40: Synthesis of salt-type graft copolymers A-37 to A-40)
First, in the same manner as in Synthesis Example 19, graft copolymer A-19 was synthesized.
Instead of the block copolymer A-1 in Synthesis Example 21, the graft copolymer A-19 (the graft copolymer before the salt formation of the salt type graft copolymers A-37 to A-40, and the graft copolymer) Salt type graft copolymer A-37 to A-40 solutions were obtained in the same manner as in Synthesis Example 23 except that the same compound A-19 was used.
In salt-type graft copolymers A-37 to A-40, the amine value, acid value, and amine value, acid value, and Tg of the graft copolymer before salt formation are shown. It is shown in 2.

(Synthesis Example 41: Synthesis of salt-type graft copolymer A-41)
The salt-type graft copolymer described in Production Example 11 of Patent Document 2 (JP 2013-250446 A) is synthesized with reference to Synthesis Example 9 and Production Example 11 of Patent Document 2, and salt-type graft copolymer A combined A-41 solution was obtained. Specifically, it was prepared as follows.
(1) Synthesis of macromonomer A reactor equipped with a cooling pipe, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 160.0 parts by mass of PGMEA and stirred at a temperature of 90 ° C. under a nitrogen stream. Warmed to. A mixed solution of MMA 100.0 parts by mass, BMA 60.0 parts by mass, BzMA 40.0 parts by mass, 2-mercaptoethanol 8.0 parts by mass, PGMEA 60 parts by mass, AIBN 2.0 parts by mass was dropped over 1.5 hours, The reaction was further continued for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., 17.48 parts by weight of Karenz MOI (manufactured by Showa Denko KK), 0.25 parts by weight of dibutyltin dilaurate, p-methoxyphenol A macromonomer was obtained by adding 0.25 mass part and 20 mass parts of PGMEA, and stirring for 3 hours. The obtained macromonomer solution was reprecipitated in hexane, purified by filtration and vacuum drying, and macromonomer C was obtained. The obtained macromonomer C had a weight average molecular weight Mw of 4000.
(2) Synthesis of graft polymer A reactor equipped with a cooling pipe, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 129.8 parts by mass of PGMEA and stirred at a temperature of 85. Warmed to ° C. A mixed solution of 33.4 parts by mass of the macromonomer C, 16.7 parts by mass of DMAPAA (manufactured by Kojin Co., Ltd.), 1.24 parts by mass of n-dodecyl mercaptan, 20.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN is 1 After dripping over 5 hours and heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and further aging at the same temperature for 1 hour. A polymer solution was obtained. The obtained graft copolymer solution was reprecipitated in hexane, and purified by filtration and vacuum drying. The obtained graft copolymer had an amine value of 122 mgKOH / g and a weight average molecular weight Mw of 11,200.
(3) Synthesis of salt-type graft copolymer A-41 In a 100 mL round bottom flask, 10.0 parts by mass of the above graft copolymer was dissolved in 63.15 parts by mass of PGMEA and represented by the general formula (3). 2-methacryloylethyl acid phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) 5.78 parts by mass (the compound represented by the general formula (3) is a graft copolymer) 1.0 mol) with respect to 1 mol of the combined DMAPAA unit, and the mixture is stirred at a reaction temperature of 40 ° C. for 20 hours to obtain a salt-type graft copolymer A-41 (Tg 80 ° C.) solution having a solid content of 20% by mass. Obtained.
Since light ester P-2M is a monovalent acid and the acidic group is used for salt formation, the acid value of the graft copolymer after salt formation is the same as that of the graft copolymer before salt formation. The amine value after salt formation was calculated as follows.
Into an NMR sample tube, 1 g of a solution prepared by mixing 9 parts by mass of salt-type graft copolymer A-41 (solid after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was added, and the 13C-NMR spectrum was measured by nuclear magnetic resonance. Using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was performed under conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of amino groups salted to the total number of amino groups was calculated, and it was confirmed that all amino groups were salted. Since there was no amino group of DMAPAA that did not form a salt, the amine value after salt formation was calculated to be 0 mgKOH / g.

(Synthesis Example 42: Synthesis of alkali-soluble resin A solution)
The polymerization tank was charged with 300 parts by mass of PGMEA and heated to 100 ° C. in a nitrogen atmosphere, and then 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA) and perbutyl. 6 parts by mass of O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining 100 ° C., and after 2 hours from the completion of dropping of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added and the temperature was raised to 110 ° C., then 0.8 parts by mass of triethylamine was added, and the mixture was heated at 110 ° C. for 15 hours. By addition reaction, an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH / g, solid content 40% by mass) was obtained.
The weight average molecular weight of the alkali-soluble resin was measured by a Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070.

Example 1
(1) Production of colorant dispersion G-1
1.95 parts by mass of the block copolymer A-1 of Synthesis Example 1 as a dispersant and C.I. I. Pigment Green 58 (PG58) 13.0 parts by mass, 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 68.8 parts by mass of PGMEA, and a particle size of 2.0 mm zirconia beads 100 parts by mass Is put into a mayonnaise bin and shaken with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour as a preliminary crushing, then the zirconia beads having a particle size of 2.0 mm are taken out and 200 parts by mass of zirconia beads having a particle size of 0.1 mm In the same manner, as this crushing, dispersion was performed for 4 hours with a paint shaker to obtain a colorant dispersion G-1.

(2) Production of Photosensitive Colored Resin Composition G-1 for Color Filter Alkali-soluble resin A obtained in Synthesis Example 42, 11.86 parts by mass of colorant dispersion G-1 obtained in (1) above 0.67 parts by mass of the solution, 0.63 parts by mass of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morphol 0.095 parts by mass of linopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.063 parts by mass, fluorosurfactant (trade name Megafac R-08MH, manufactured by DIC Corporation) 0.07 parts by mass, PG 6.61 parts by mass of MEA was added to obtain a photosensitive colored resin composition G-1 for color filter.

(Examples 2 to 24)
(1) Production of Color Material Dispersions G-2 to G-24 In Example 1 (1), instead of the block copolymer A-1, Synthesis Example 2 was carried out as shown in Tables 3 to 4, respectively. Block copolymer A-2 to A-3, block copolymers A-6 to A-15 of synthesis examples 6 to 15, salt type block copolymers A-21 to A of synthesis examples 21 to 31 The -31 solution was used so that the solid content would be the same as that of the block copolymer A-1, and the amount of PGMEA was adjusted so that the total would be 100 parts by mass. Similarly, colorant dispersions G-2 to G-24 were obtained.
(2) Production of Photosensitive Colored Resin Compositions G-2 to G-24 for Color Filter In (2) of Example 1, instead of the color material dispersion G-1, the above color material dispersion G-2, respectively. Except having used -G-24, it carried out similarly to (2) of Example 1, and obtained photosensitive colored resin composition G-2-G-24 for color filters.

(Comparative Examples 1-17)
(1) Production of Comparative Colorant Dispersions CG-1 to CG-17 In Example 1 (1), instead of the block copolymer A-1, as shown in Tables 3 to 4, respectively, Synthesis Examples Block copolymers A-4 and A-5 of 4, 5; Block copolymers A-16 to A-18 of Synthesis Examples 16 to 18; Graft copolymers A-19 to A- of Synthesis Examples 19 to 20 20, salt type random copolymer A-32 of synthesis example 32, salt type block copolymer A-33 to A-36 solution of synthesis examples 33 to 36, salt type graft copolymer A of synthesis examples 37 to 41 The -37 to A-41 solutions were used in Example 1 except that the solid content was the same as that of the block copolymer A-1 and that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. Comparative colorant dispersions CG-1 to CG-17 were obtained in the same manner as (1).
(2) Production of Photosensitive Colored Resin Compositions CG-1 to CG-17 for Comparative Color Filter In Example 1 (2), instead of the color material dispersion G-1, the above comparative color material dispersion CG, respectively. Except having used -1 to CG-17, it carried out similarly to (2) of Example 1, and obtained photosensitive colored resin composition CG-1 to CG-17 for comparison color filters.

[Evaluation method]
<Evaluation of dispersion stability of colorant dispersion>
For the colorant dispersions obtained in Examples and Comparative Examples, the viscosity immediately after preparation and after storage for 30 days at 25 ° C. are measured, the rate of change in viscosity is calculated from the viscosity before and after storage, and the viscosity stability is evaluated. did. The viscosity was measured at 25.0 ± 0.5 ° C. using a vibration viscometer (model name: FVM80A-STC, manufactured by Seconic Co., Ltd.). The results are shown in Tables 3-4.
(Dispersion stability evaluation criteria)
A: Change rate of viscosity before and after storage is less than 15% B: Change rate of viscosity before and after storage is 15% or more and less than 40% C: Change rate of viscosity before and after storage is 40% or more and less than 80% D: Before and after storage Viscosity change rate is 80% or more However, this is a value when the color material is 13% by mass with respect to the total mass including the solvent of the color material dispersion.
Even if the evaluation result is B, the color material dispersion can be used practically, but if the evaluation result is A, the color material dispersion is excellent in dispersion stability.

<Optical performance evaluation, contrast evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After coating using a coater, the colored layer was formed by drying at 80 ° C. for 3 minutes using a hot plate. This colored layer was irradiated with 60 mJ / cm ² of ultraviolet rays using an ultrahigh pressure mercury lamp.
Next, the colored substrate was post-baked for 30 minutes in a clean oven at 230 ° C., and the contrast, chromaticity (x, y), and luminance (Y) of the obtained colored substrate were compared with a contrast measuring device CT-1B manufactured by Aisaka Electric. And Olympus microspectrophotometer OSP-SP200.

(Contrast evaluation criteria)
A: Green over 7300, Red over 4000, Blue over 6800 B: Green over 6600 over 7300, Red over 3300 over 4000, Blue over 6100 over 6800 C: Green over 5700 over 6600, Red over 2600 Exceeding 3300 or less, Blue exceeding 5400, 6100 or less D: Green is 5700 or less, Red is 2600 or less, Blue is 5400 or less. This is the value when y = 0.135.
Even if the evaluation result is B, the photosensitive colored resin composition for a color filter can be used practically, but if the evaluation result is A, the photosensitive colored resin composition for a color filter is more suitable for higher contrast.

<Development adhesion evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After coating with a coater to form a colored layer having a thickness of 1.6 μm after post-baking, the coated layer was dried at 80 ° C. for 3 minutes using a hot plate to form a colored layer. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using a super high pressure mercury lamp through a photomask having a mask opening width of ² to 80 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The substrate after development was observed with an optical microscope, and the presence or absence of a colored layer with respect to the mask opening line width was observed. A result is combined with Tables 3-4 and shown.
(Development adhesion evaluation criteria)
A: A colored layer was observed in a portion having a mask opening line width of less than 20 μm B: A colored layer was observed in a portion having a mask opening line width of 20 μm or more and less than 50 μm C: A portion having a mask opening line width of 50 μm or more and less than 80 μm A colored layer was observed in D: A colored layer was not observed in a portion having a mask opening line width of 80 μm or less. Even if the evaluation result was B, the photosensitive colored resin composition for color filters could be used practically, but the evaluation result was A. Then, the photosensitive colored resin composition for color filters is suitable for higher definition.

<Development residue evaluation>
The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were each spinned on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After coating using a coater, the coating was dried at 80 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. After observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer by visual observation, the glass substrate is thoroughly wiped with a lens cleaner (trade name Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.), The coloring degree of the lens cleaner was visually observed. A result is combined with Tables 3-4 and shown.
(Development residue evaluation criteria)
A: The development residue was not visually confirmed and the lens cleaner was not colored at all. B: The development residue was not visually confirmed and the lens cleaner was slightly colored. C: The development residue was slightly confirmed visually. D: The color of the lens cleaner was slightly confirmed. D: The development residue was confirmed by visual observation, and the color of the lens cleaner was confirmed. If the evaluation result is B, the photosensitive colored resin composition for color filters is suitable for higher definition, and if the evaluation result is A, the photosensitive colored resin composition for color filters is more suitable for higher definition. ing.

<Solvent resolubility evaluation>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for a color filter obtained in Examples and Comparative Examples and applied to a 1 cm portion of the glass substrate. The pulled-up glass substrate was put into a constant temperature and humidity chamber so that the glass surface was horizontal, and dried at a temperature of 23 ° C. and a humidity of 80% RH for 30 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dried coating film was visually discriminated and evaluated. A result is combined with Tables 3-4 and shown.
(Solvent re-solubility evaluation criteria)
A: The dried coating film was completely dissolved B: The dried coating film flakes were formed in the solvent, and the solution was colored C: The dried coating film flakes were formed in the solvent, and the solution was not colored D: In the solvent If the development residue evaluation criteria are A and B, the solvent resolubility is evaluated as good and can be used practically without any problem.

[Summary of results]
From the results of Tables 1 to 4, as a dispersant, the block copolymer (P1) containing the structural unit represented by the general formula (I) and the general formula (I) of the block copolymer A salt in which at least a part of the terminal nitrogen moiety of the structural unit represented and one or more compounds selected from the group consisting of compounds represented by the following general formulas (1) to (3) form a salt Dispersant which is at least one type of block copolymer (P2), wherein the block copolymer (P1) has an amine value of 35 to 110 mgKOH / g, and the dispersant has a glass transition temperature of 30 ° C. or higher It was clarified that the color material dispersions of Examples 1 to 24 using No. 1 were excellent in color material dispersion stability even when the amount of the dispersant was reduced. It is considered that the dispersant containing the structural unit represented by the general formula (I) of the present application has high basicity at the terminal nitrogen site and strong adsorptivity to the coloring material.
In addition, the photosensitive colored resin compositions for color filters of Examples 1 to 24 prepared using the color material dispersions of Examples 1 to 24 are excellent in color material dispersibility and thus excellent in contrast of the colored layer. The development adhesion was excellent and the solvent resolubility was excellent, while the generation of development residues was suppressed.
A comparison between Example 11 and Examples 1 to 10, 12 and 13 revealed that the development adhesion was improved particularly in the case of a copolymer containing a structural unit derived from a hydroxyl group-containing monomer.
Among them, the photosensitive colored resin compositions for color filters of Examples 4 to 5 using a block copolymer containing a structural unit having an acidic functional group in the B block that imparts solvophilicity improve the effect of suppressing development residue. It was revealed that
Among them, the photosensitive colored resin compositions for color filters of Examples 14 to 24 using the salt type block copolymer were particularly excellent in colorant dispersibility, and the contrast of the resulting colored layer was particularly excellent. .
In particular, when a block copolymer containing a structural unit having an acidic functional group was used for the B block imparting solvophilicity, and the salt type block copolymer was further used, the acid value increased in Examples 23-24. It has been clarified that the photosensitive colored resin composition for color filters further improves the development residue suppression effect even when the development residue suppression effect is greater than that of Example 5.

On the other hand, although the glass transition temperature of the dispersant is 30 ° C. or higher, Comparative Example 1 in which the amine value is lower than the specific value of the present application has poor color material dispersion stability, and the contrast of the colored layer is inferior, Furthermore, the development residue was outside the practical level range. Moreover, although the glass transition temperature of a dispersing agent is 30 degreeC or more, the comparative example 2 whose amine value is higher than the specific value of this application has the solvent re-dissolution property outside the practical level range.
Moreover, it was clarified that Comparative Example 3 in which the glass transition temperature of the dispersant is less than 30 ° C. is inferior in development adhesion. Comparative Example 8 using a copolymer corresponding to Production Example 1 of Patent Document 1 also had a glass transition temperature of less than 30 ° C. and poor development adhesion. Since the copolymer corresponding to Production Example 1 of Patent Document 1 is a random copolymer, the colorant dispersion stability is poor and the contrast of the colored layer is poor.
Comparative Example 4 using a block copolymer or a salt-type block copolymer containing a structural unit derived from dimethylaminoethyl methacrylate instead of the structural unit represented by the general formula (I) as a dispersant Nos. 5 and 9 to 12 were inferior in the color material dispersion stability and inferior in the contrast of the colored layer.
In addition, Comparative Examples 6, 7, and 13 to 17 using the graft copolymer or the salt-type graft copolymer, all of which contain the structural unit represented by the general formula (I) as the dispersant, are the invention of the present application. Compared to the color material dispersion stability was inferior. Since Comparative Example 17 was inferior in development adhesion and the amine value was higher than the specific value of the present application, the solvent resolubility was outside the practical level range.

Next, the experiment which investigated about the influence which dispersing agent content has on the shape and physical property of a colored layer is shown.
Table 5 compares the dispersion stability and development residue, evaluation of chipping of the colored pattern shown below, and evaluation of water stain with the photosensitive colored resin composition for color filter of Example 1 above. The result performed with respect to the photosensitive colored resin composition for color filters of Example 4, Comparative Example 6, and Comparative Example 7 is shown. In Example 1, Comparative Example 4, Comparative Example 6, and Comparative Example 7, D / P (mass ratio) when the dispersant content is D and the colorant content is P is 0.15, respectively. It is an example. In Example 1, the color material dispersion stability evaluation is as high as A, whereas in Comparative Example 4, Comparative Example 6, and Comparative Example 7, the color material dispersion stability evaluation is inferior to D and C, respectively. Since Example 1 and Comparative Example 4, Comparative Example 6 and Comparative Example 7 have the same D / P ratio and other compositions, the evaluation of the lack of the colored pattern and the evaluation of water stain are equivalent. is there. On the other hand, in order to increase the colorant dispersion stability of the dispersants of Comparative Example 4, Comparative Example 6 and Comparative Example 7 to the same level as in Example 1, the following Comparative Example 18, Comparative Example 19 and Comparative Example 20 were used. As shown, it has been clarified that it cannot be achieved unless the D / P ratio is increased. However, when the D / P ratio is increased, although the dispersion stability is increased, it has been clarified that all of the lack of the coloring pattern, the water stain, and the development residue are deteriorated.

(Comparative Example 18)
(1) Production of Comparative Color Material Dispersion CG-18 In Comparative Example 4 (1), the block copolymer A- was prepared so that the D / P ratio was 0.35 while keeping the same color material amount. Comparative colorant dispersion CG-18 was obtained in the same manner as (1) of Comparative Example 4 except that the content of 17 was increased and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of photosensitive colored resin composition CG-18 for comparative color filter In Comparative Example 4 (2), instead of the color material dispersion CG-4, the comparative color material dispersion G-18 was changed. 0.44 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.41 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and 7. PGMEA Except having set it as 05 mass parts, it carried out similarly to (2) of the comparative example 4, and obtained the photosensitive colored resin composition CG-18 for comparative color filters.

(Comparative Example 19)
(1) Production of Comparative Color Material Dispersion CG-19 In Comparative Example 6 (1), the graft copolymer A- was prepared so that the D / P ratio was 0.25 while maintaining the same color material amount. Comparative colorant dispersion CG-19 was obtained in the same manner as (1) of Comparative Example 6 except that the content of 19 was increased and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of Photosensitive Colored Resin Composition G-19 for Comparative Color Filter In (2) of Comparative Example 6, the color material dispersion liquid CG-6 was replaced with the above comparative color material dispersion liquid G-19. 0.56 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.52 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and 6. PGMEA. Except that it was 84 mass parts, it carried out similarly to (2) of the comparative example 6, and obtained the photosensitive colored resin composition CG-19 for comparative color filters.

(Comparative Example 20)
(1) Production of Comparative Color Material Dispersion CG-20 In Comparative Example 7 (1), the graft copolymer A- was prepared so that the D / P ratio was 0.25 while maintaining the same color material amount. Comparative colorant dispersion CG-20 was obtained in the same manner as (1) of Comparative Example 7 except that the content of 20 was increased and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.
(2) Production of photosensitive colored resin composition G-20 for comparative color filter In Comparative Example 7 (2), instead of the color material dispersion CG-7, the comparative color material dispersion G-20 was changed. 0.56 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.52 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and 6. PGMEA. Except that it was 84 mass parts, it carried out similarly to (2) of the comparative example 7, and obtained the photosensitive colored resin composition CG-20 for comparative color filters.

(Example 25)
In the same manner as in Example 1 (1), a colorant dispersion G-1 was obtained.
In the production of the photosensitive colored resin composition G-1 for color filter (2) in Example 1, the photoinitiator was 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. 0.016 parts by mass of (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) was added to ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- (O-acetyloxime) (trade name Irgacure OXE02, manufactured by BASF Japan Ltd.) was used in the same manner as in Example 1 to obtain a photosensitive colored resin composition G-25 for a color filter. .

(Example 26)
In the same manner as in Example 1 (1), a colorant dispersion G-1 was obtained.
In the production of the photosensitive colored resin composition G-1 for color filter (2) in Example 1, the photoinitiator was 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. Example 1 except that 0.016 parts by mass of (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) was changed to ADEKA Adekaoptomer N-1919, which is an oxime ester photoinitiator. In the same manner as above, a photosensitive colored resin composition G-26 for color filters was obtained.

(Comparative Example 21)
In the same manner as in Comparative Example 18 (1), a colorant dispersion CG-21 was obtained.
In the production of the photosensitive colored resin composition CG-18 for the color filter of Comparative Example 18 (2), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 was used as the photoinitiator. 0.016 parts by mass of (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) was added to ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- (O-acetyloxime) (trade name Irgacure OXE02, manufactured by BASF Japan Ltd.) was used in the same manner as Comparative Example 18 to obtain a photosensitive colored resin composition CG-21 for color filters. .

(Comparative Example 22)
In the same manner as in Comparative Example 19 (1), a colorant dispersion CG-22 was obtained.
In the production of the photosensitive colored resin composition CG-19 for the color filter of Comparative Example 19 (2), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 was used as the photoinitiator. 0.016 parts by mass of (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) was added to ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- (O-acetyloxime) (trade name Irgacure OXE02, manufactured by BASF Japan Ltd.) was used in the same manner as in Comparative Example 19 to obtain a photosensitive colored resin composition CG-22 for a color filter. .

<Evaluation of missing colored pattern>
The photosensitive colored resin composition obtained in each Example and each Comparative Example was subjected to a thickness of 1. after post-baking on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. After coating with a film thickness to form a 6 μm colored layer, it is dried at 80 ° C. for 3 minutes using a hot plate, and this colored layer is passed through a striped photomask having a mask opening width of 90 μm with an ultrahigh pressure mercury lamp. A colored layer was formed on the glass substrate by exposing to 30 mJ / cm ² with UV light. Next, 0.05 wt% potassium (KOH) is spin-developed as a developer, and the developer is subjected to an indirect solution for 60 seconds and then washed with pure water to form a pattern with a line width as shown below. did.
The edge of the colored pattern after exposure and development formed on the glass substrate was observed using an optical microscope, and the lack of the colored pattern was evaluated.
(Evaluation criteria)
A: Color pattern defects were not observed B: Color pattern defects were slightly observed C: Color pattern defects were observed a lot D: Color pattern defects were observed significantly a color pattern defect was observed If the evaluation criterion is A or B, it is evaluated that the lack of the colored pattern is sufficiently suppressed, and can be used practically without any problem.

<Water stain evaluation>
The photosensitive colored resin composition obtained in each Example and each Comparative Example was subjected to a thickness of 1. after post-baking on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. After coating with a film thickness that forms a 6 μm colored layer, it is dried at 80 ° C. for 3 minutes using a hot plate, and irradiated with 60 mJ / cm ² of UV light using an ultrahigh pressure mercury lamp without a photomask. Thus, a colored layer was formed on the glass substrate. Next, spin development is performed using 0.05 wt% potassium (KOH) as a developer, the developer is subjected to an indirect solution for 60 seconds and then washed with pure water, and the washed substrate is rotated for 10 seconds to remove water. Immediately after centrifugation, the contact angle of pure water was measured as described below to evaluate water stain. In addition, if the contact angle of pure water is 65 degrees or more, it is evaluated that the water stain that causes a problem of unevenness in the appearance inspection does not occur.
The contact angle of pure water was measured by dropping 1.0 μL of pure water on the surface of the colored layer immediately after removing the water by centrifugation, and determining the static contact angle 10 seconds after the landing according to the θ / 2 method. Measured. The measuring device was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.
(Evaluation criteria)
A: Contact angle of 80 degrees or more B: Contact angle of 65 degrees or more and less than 80 degrees C: Contact angle of 50 degrees or more and less than 65 degrees D: Contact angle of less than 50 degrees Water stain is sufficient if the water stain evaluation standard is A or B Therefore, it can be used without any practical problem.

[Summary of results]
In order to increase the colorant dispersion stability of the dispersants of Comparative Example 4, Comparative Example 6 and Comparative Example 7 to the same level as in Example 1, as shown in Comparative Example 18, Comparative Example 19 and Comparative Example 20 below. It has been clarified that it cannot be achieved without increasing the D / P ratio. As described above, when the dispersant content is increased to such an extent that the color material dispersion stability is improved, the color material dispersion stability becomes as excellent as that of the present invention, but the photosensitive coloring It has been clarified that the content of the binder component contained in the resin composition has to be relatively low, causing problems such as lack of a colored pattern and water stain.
Moreover, instead of the photoinitiator used in Example 1, Example 25 and Example 26 using an oxime ester photoinitiator have a high effect of suppressing the occurrence of color pattern chipping and water stain. Was revealed. Similarly, Comparative Example 21 and Comparative Example 22 using an oxime ester photoinitiator had a lack of coloring pattern compared to Comparative Example 18, Comparative Example 19 and Comparative Example 20 which did not use an oxime ester photoinitiator. Although generation | occurrence | production of the water stain was reduced, it was clarified that it was inferior to the effect of this invention.

(Example 27)
(1) Production of colorant dispersion G-27
1.95 parts by mass of the salt type block copolymer A-22 (0.5 molar equivalent of phenylphosphinic acid) of Synthesis Example 22 as a dispersant and C.I. I. Pigment Green 58 (PG58) 13.0 parts by mass, 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 68.8 parts by mass of PGMEA, and a particle size of 2.0 mm zirconia beads 100 parts by mass Is put into a mayonnaise bin and shaken with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour as a preliminary crushing, then the zirconia beads having a particle size of 2.0 mm are taken out and 200 parts by mass of zirconia beads having a particle size of 0.1 mm In the same manner, as this pulverization, dispersion was performed for 4 hours with a paint shaker to obtain a colorant dispersion G-27.

(2) Production of photosensitive colored resin composition G-27 for color filter 11.40 parts by mass of colorant dispersion G-27 obtained in (1) above, alkali-soluble resin A obtained in Synthesis Example 42 0.67 parts by mass of the solution, 0.63 parts by mass of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morphol 0.095 parts by mass of linopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.063 parts by mass, fluorosurfactant (trade name Megafac R-08MH, manufactured by DIC Corporation) 0.07 parts by mass, 6.61 parts by mass of PGMEA was added to obtain a photosensitive colored resin composition G-27 for color filters.

(Comparative Example 23)
(1) Production of colorant dispersion CG-23
In Example 27, the salt-type block copolymer of Synthesis Example 33 was used instead of the salt-type block copolymer A-22 of Synthesis Example 22 (DMAPMA-derived structural unit, 0.5 molar equivalent of phenylphosphinic acid) as a dispersant. A colorant dispersion CG-23 was obtained in the same manner as in Example 27 except that A-33 (DMMA-derived structural unit, 0.5 molar equivalent of phenylphosphinic acid) was used.
(2) Production of photosensitive colored resin composition CG-23 for color filter In Example 27, the color material dispersion CG-23 obtained in (1) above was used instead of the color material dispersion G-27. In the same manner as in Example 27 except for the above, a photosensitive colored resin composition CG-23 for color filter was obtained.

(Comparative Example 24)
(1) Production of colorant dispersion CG-24
In Comparative Example 23 (1), the content of the salt-type block copolymer A-33 was increased so that the D / P ratio was 0.35 while the color material amount was the same, and the total amount was 100. A comparative color material dispersion CG-24 was obtained in the same manner as in (1) of Comparative Example 23 except that the amount of PGMEA was adjusted to be part by mass.
(2) Production of Photosensitive Colored Resin Composition CG-24 for Comparative Color Filter In Comparative Example 23 (2), instead of the color material dispersion CG-23, the comparative color material dispersion CG-24 was changed. 0.44 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.41 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and 7. PGMEA Except having set it as 05 mass parts, it carried out similarly to (2) of the comparative example 23, and obtained the photosensitive colored resin composition CG-24 for comparative color filters.

(Example 28)
(1) Production of colorant dispersion B-1
1.95 parts by mass of the salt type block copolymer A-27 (benzyl bromide 0.2 molar equivalent) of Synthesis Example 27 as a dispersant and C.I. I. Pigment Blue 15: 6 (PB15: 6) 13.0 parts by mass, 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 68.8 parts by mass of PGMEA, and a particle size of 2.0 mm zirconia 100 parts by mass of beads are put into a mayonnaise bin, shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a pre-crush, then take out zirconia beads having a particle size of 2.0 mm, and zirconia having a particle size of 0.1 mm 200 parts by mass of beads were added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a colorant dispersion B-1.

(2) Production of photosensitive colored resin composition B-1 for color filter 8.59 parts by mass of colorant dispersion B-1 obtained in (1) above, alkali-soluble resin A obtained in Synthesis Example 42 1.12 parts by mass of the solution, 1.04 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpho 0.158 parts by mass of linopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.105 parts by mass, fluorosurfactant (trade name MegaFac R-08MH, manufactured by DIC Corporation) 0.07 parts by mass, PGM 8.91 parts by mass of EA was added to obtain a photosensitive colored resin composition B-1 for color filters.

(Comparative Example 25)
(1) Production of colorant dispersion CB-1
In Example 28, instead of the salt-type block copolymer A-27 (DMAPMA-derived structural unit, benzyl bromide 0.2 molar equivalent) of Synthesis Example 27 as a dispersant, the salt-type block copolymer A of Synthesis Example 35 was used. A colorant dispersion CB-1 was obtained in the same manner as in Example 28 except that -35 (DMMA-derived structural unit, benzyl bromide 0.2 molar equivalent) was used.
(2) Production of photosensitive colored resin composition CB-1 for color filter In Example 28, the color material dispersion CB-1 obtained in (1) above was used instead of the color material dispersion B-1. In the same manner as in Example 28 except for the above, a photosensitive colored resin composition CB-1 for color filter was obtained.

(Comparative Example 26)
(1) Production of colorant dispersion CB-2
In (1) of Comparative Example 25, the content of the salt-type block copolymer A-35 was increased so that the D / P ratio was 0.35 while keeping the same color material amount, and the total amount was 100. A comparative color material dispersion CB-2 was obtained in the same manner as in (1) of Comparative Example 25 except that the amount of PGMEA was adjusted to be part by mass.
(2) Production of Photosensitive Colored Resin Composition CB-2 for Comparative Color Filter In Comparative Example 25 (2), instead of the color material dispersion CB-1, the above-mentioned comparison color material dispersion CB-2 was changed. 0.95 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.89 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and 9. Except having been 23 mass parts, it carried out similarly to (2) of the comparative example 25, and obtained the photosensitive colored resin composition CB-2 for comparative color filters.

For Examples 27 to 28 and Comparative Examples 23 to 26, the color material dispersion stability, contrast, and optical performance were evaluated in the same manner as in Example 1, and the heat resistance was also evaluated as follows. It was. The evaluation results are shown in Table 6.
<Evaluation of heat resistance (color difference ΔEab)>
The spin-coater was applied to the photosensitive coloring compositions for color filters obtained in Examples and Comparative Examples on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After post-baking using a C light source with a C light source, green is applied to a thickness that forms y = 0.500 and blue is y = 0.135, followed by drying at 80 ° C. for 3 minutes using a hot plate By doing so, a colored layer was formed. This colored layer was irradiated with 60 mJ / cm ² of ultraviolet rays using an ultrahigh pressure mercury lamp. The chromaticity (x, y), luminance (Y), L, a, and b (L ₀ , a ₀ , b ₀ ) of the obtained colored substrate were measured using an Olympus microspectrophotometer OSP-SP200.
Next, the colored substrate is post-baked for 30 minutes in a clean oven at 230 ° C., and the chromaticity (x, y), luminance (Y), L, a, b (L ₁ , a ₁ , b ₁ ) was measured again.
As the heat resistance evaluation, the color difference (ΔEab) before and after post-baking was calculated from the following formula.
ΔEab = {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² } ^1/2

(Example 29)
(1) Production of coloring material dispersion R-1
1.95 parts by mass of the salt type block copolymer A-27 (benzyl bromide 0.2 molar equivalent) of Synthesis Example 27 as a dispersant and C.I. I. Pigment Red 254 (PR254) 13.0 parts by mass, 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 68.8 parts by mass of PGMEA, and a particle size of 2.0 mm zirconia beads 100 parts by mass Is put into a mayonnaise bin and shaken with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour as a preliminary crushing, then the zirconia beads having a particle size of 2.0 mm are taken out and 200 parts by mass of zirconia beads having a particle size of 0.1 mm In the same manner, as this crushing, dispersion was performed for 4 hours with a paint shaker to obtain a colorant dispersion R-1.

(2) Production of photosensitive colored resin composition R-1 for color filter Alkali-soluble resin A obtained in Synthesis Example 42, 11.86 parts by mass of colorant dispersion R-1 obtained in (1) above 0.67 parts by mass of the solution, 0.63 parts by mass of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morphol 0.095 parts by mass of linopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.063 parts by mass, fluorosurfactant (trade name Megafac R-08MH, manufactured by DIC Corporation) 0.07 parts by mass, PG 6.61 parts by mass of MEA was added to obtain a photosensitive colored resin composition R-1 for color filters.

(Comparative Example 27)
(1) Production of colorant dispersion CR-1
In Example 29, instead of the salt-type block copolymer A-27 (DMAPMA-derived structural unit, benzyl bromide 0.2 molar equivalent) of Synthesis Example 27 as a dispersant, the salt-type block copolymer A of Synthesis Example 35 was used. A colorant dispersion CR-1 was obtained in the same manner as in Example 29 except that -35 (DMMA-derived structural unit, benzyl bromide 0.2 molar equivalent) was used.
(2) Production of photosensitive colored resin composition CR-1 for color filter In Example 29, the color material dispersion R-2 obtained in (1) above was used instead of the color material dispersion R-1. A photosensitive colored resin composition CR-1 for color filter was obtained in the same manner as in Example 29 except that.

(Comparative Example 28)
(1) Production of colorant dispersion CR-2
In Comparative Example 27 (1), the content of the salt-type block copolymer A-35 was increased so that the D / P ratio was 0.35 while the color material amount was the same, and the total amount was 100. A comparative color material dispersion CR-2 was obtained in the same manner as in (1) of Comparative Example 27 except that the amount of PGMEA was adjusted to be part by mass.
(2) Production of photosensitive colored resin composition CR-2 for comparative color filter In Comparative Example 27 (2), instead of the color material dispersion CR-1, the color material dispersion was changed to the above-mentioned comparison color material dispersion CR-2. 0.44 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.41 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and 7. PGMEA Except having set it as 05 mass parts, it carried out similarly to (2) of the comparative example 27, and obtained photosensitive colored resin composition CR-2 for comparative color filters.

(Example 30)
(1) Production of coloring material dispersion Y-1
1.95 parts by mass of the salt-type block copolymer A-21 (0.5 molar equivalent of phenylphosphinic acid) of Synthesis Example 21 as a dispersant and C.I. I. 13.0 parts by mass of Pigment Yellow 138 (PY138), 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 68.8 parts by mass of PGMEA, 100 parts by mass of 2.0 mm zirconia beads Is put into a mayonnaise bin and shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a preliminary crushing, then the zirconia beads having a particle size of 2.0 mm are taken out, and 200 parts by mass of zirconia beads having a particle size of 0.1 mm In the same manner, as this crushing, dispersion was performed for 4 hours with a paint shaker to obtain a colorant dispersion Y-1.

(2) Production of photosensitive colored resin composition Y-1 for color filter Alkali-soluble resin A obtained in Synthesis Example 42, 11.86 parts by mass of colorant dispersion Y-1 obtained in (1) above 0.67 parts by mass of the solution, 0.63 parts by mass of polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morphol 0.095 parts by mass of linopropan-1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (photoinitiator: trade name Irgacure 369, manufactured by BASF Japan) 0.063 parts by mass, fluorosurfactant (trade name Megafac R-08MH, manufactured by DIC Corporation) 0.07 parts by mass, PG 6.61 parts by mass of MEA was added to obtain a photosensitive colored resin composition Y-1 for color filters.

(Comparative Example 29)
(1) Production of colorant dispersion CY-1
In Example 30, the salt type block copolymer of Synthesis Example 33 was used instead of the salt type block copolymer A-22 of Synthesis Example 22 (DMAPMA-derived structural unit, 0.5 molar equivalent of phenylphosphinic acid) as a dispersant. A colorant dispersion CY-1 was obtained in the same manner as in Example 30 except that A-33 (DMMA-derived structural unit, 0.5 molar equivalent of phenylphosphinic acid) was used.
(2) Production of photosensitive colored resin composition Y-2 for color filter In Example 30, the color material dispersion CY-1 obtained in (1) above was used instead of the color material dispersion Y-1. In the same manner as in Example 30, except for the above, a photosensitive colored resin composition CY-1 for color filter was obtained.

(Comparative Example 30)
(1) Production of colorant dispersion CY-2
In Comparative Example 29 (1), the content of the salt-type block copolymer A-33 was increased so that the D / P ratio was 0.35 while the color material amount was the same, and the total amount was 100. A comparative color material dispersion CY-2 was obtained in the same manner as in (1) of Comparative Example 29 except that the amount of PGMEA was adjusted to be part by mass.
(2) Production of Photosensitive Colored Resin Composition CY-2 for Comparative Color Filter In Comparative Example 29 (2), instead of the color material dispersion CY-1, the above-mentioned comparison color material dispersion CY-2 was changed. 0.44 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.41 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and 7. PGMEA Except having set it as 05 mass parts, it carried out similarly to (2) of the comparative example 29, and obtained the photosensitive colored resin composition CY-2 for comparative color filters.

For Examples 29-30 and Comparative Examples 27-30, the colorant dispersion stability and contrast were evaluated in the same manner as in Example 1, and the pigment aggregates after high-temperature heating were precipitated as described below. Evaluation was also performed. Table 7 shows the evaluation results.
<Evaluation of precipitation of pigment aggregate after heating at high temperature>
The spin-coater was applied to the photosensitive coloring compositions for color filters obtained in Examples and Comparative Examples on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After the post-baking process, the film was applied to form a colored layer having a thickness of 1.6 μm, and then dried at 80 ° C. for 3 minutes using a hot plate to form a colored layer. This colored layer was irradiated with 60 mJ / cm ² of ultraviolet rays using an ultrahigh pressure mercury lamp. The colored layer of the obtained colored substrate was observed with an optical microscope.
Next, the colored substrate was post-baked for 30 minutes in a clean oven at 230 ° C., and the colored layer of the obtained colored substrate was again observed with an optical microscope to confirm the presence or absence of pigment aggregate precipitation due to post-baking.

[Summary of results]
From the results in Table 7, the colorant dispersions of Examples 29 to 30 using the salt type block copolymer containing the structural unit represented by the general formula (I) specified in the present invention as the dispersant are as follows. It was revealed that the colorant dispersion stability was excellent. In addition, the photosensitive colored resin compositions for color filters of Examples 29 to 30 prepared using the color material dispersions of Examples 29 to 30 not only have excellent color material dispersion stability and excellent contrast, It has been clarified that the effect of suppressing the precipitation of pigment aggregates is high after the heating step after fine dispersion.

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 (11)

A color material dispersion containing a color material, a dispersant, and a solvent,
The dispersant is at least one of the following block copolymer (P1) and the following salt-type block copolymer (P2),
P1: a block copolymer containing a structural unit represented by the following general formula (I);
P2: From the compounds represented by the following general formulas (1) to (3) and at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer (P1) A salt-type block copolymer in which a salt is formed with one or more compounds selected from the group consisting of:
A color material dispersion for a color filter, wherein the block copolymer (P1) has an amine value of 35 to 110 mgKOH / g and a glass transition temperature of the dispersant of 30 ° C. or higher.

(In General Formula (I), R ¹ and R ^{1 ′} are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, — [CH (R ⁶ ) —CH (R ⁷ ) A divalent group represented by —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or [(CH ₂ ) _y —O] _z — (CH ₂ ) _y —, R ² and R ³ are: Each independently represents a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R ² and R ³ may be bonded to each other to form a ring structure, and R ⁶ and R ⁷ are each independently A hydrogen atom or a methyl group, 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.
In General Formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R. ^e represents, and R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or benzyl group, or an alkylene having 1 to 4 carbon atoms. It represents a (meth) acryloyl group via a group. In the general formula (2), R ^b , R ^{b ′} , and R ^{b ″} each independently represent a hydrogen atom, an acidic group or an ester group thereof, a linear chain having 1 to 20 carbon atoms that may have a substituent, Represents a branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or -O- ^Rf , and ^Rf has a substituent. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or 1 carbon atom Represents a (meth) acryloyl group via an alkylene group of ˜4, X represents a chlorine atom, a bromine atom, or an iodine atom, In the general formula (3), R ^c and R ^d are each independently a hydrogen atom; , A hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Represents a vinyl group, an optionally substituted phenyl group or benzyl group, or —O—R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, A phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group via an alkylene group having 1 to 4 carbon atoms, provided that at least one of R ^c and R ^d contains a carbon atom. .)   The color material dispersion for a color filter according to claim 1, wherein the color material includes one or more selected from the group consisting of a phthalocyanine pigment, a diketopyrrolopyrrole pigment, and a quinophthalone pigment.   The color material dispersion for a color filter according to claim 1 or 2, wherein the block copolymer (P1) in the dispersant contains a structural unit derived from a hydroxyl group-containing monomer. The block copolymer (P1) in the dispersant is
(I) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer, and
(Ii) The color material dispersion for a color filter according to any one of claims 1 to 3, comprising at least one of structural units derived from a hydroxyl group and an aromatic group-containing monomer.   In the salt type block copolymer (P2), the group consisting of the general formulas (1) to (3) with respect to 1 mol of a terminal nitrogen moiety contained in the structural unit represented by the general formula (I). The color material dispersion for a color filter according to any one of claims 1 to 4, wherein 0.1 to 0.8 mol of at least one compound selected from 1 is included.   The block copolymer (P1) in the dispersant further includes a structural unit derived from a carboxy group-containing monomer, and the acid value of the block copolymer (P1) is 1 to 18 mgKOH / g, and the salt type The color material dispersion for a color filter according to any one of claims 1 to 5, wherein the block copolymer (P2) has an acid value of 1 to 55 mgKOH / g.   The photosensitive coloring resin composition for color filters containing the color material dispersion liquid as described in any one of Claims 1 thru | or 6, alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.   The photosensitive colored resin composition for color filters according to claim 7, wherein the photoinitiator contains an oxime ester.   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 photosensitive colored resin composition for a color filter according to claim 7 or 8. A color filter comprising a colored layer formed by being formed.   A liquid crystal display device comprising: the color filter according to claim 9; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.   10. An organic light emitting display device comprising the color filter according to claim 9 and an organic light emitter.

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