JP6953851B2 - Polymer dispersant and its manufacturing method, color material dispersion liquid, colored resin composition, color filter, liquid crystal display device, and light emission display device - Google Patents

Description

The embodiments of the present disclosure relate to a polymer dispersant and a method for producing the same, a color material dispersion liquid, a colored resin composition, a color filter, a liquid crystal display device, and a light emitting display device.

Many thin image display devices such as displays, so-called flat panel displays, have been put on the market because they are thinner than CRT displays and do not take up space in the depth direction. The market price is becoming more affordable year by year with the evolution of production technology, the demand is expanding further, and the production volume is also increasing year by year. In particular, color LCD TVs have almost reached the mainstream of TVs. Further, recently, a light emitting display device such as an organic light emitting display device such as an organic EL display having high visibility by self-luminous light has also attracted attention as a next-generation image display device. In terms of the performance of these image display devices, further improvement in image quality and reduction in power consumption such as improvement in contrast and color reproducibility are strongly desired.
A color filter is used in these liquid crystal display devices and light emission display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, the amount of light is controlled by electrically driving the liquid crystal, and the light passes through a color filter to express colors. Therefore, color filters are indispensable for the color expression of LCD TVs, and they also play a major role in affecting the performance of displays. Further, in the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed in the same manner as the liquid crystal display device.

As a trend in recent years, there is a demand for power saving of image display devices, and in particular, there is a demand for higher brightness of color filters in order to improve the utilization efficiency of backlights. This is a major issue especially for mobile displays (mobile phones, smartphones, tablet PCs).
Although the battery capacity has increased due to technological evolution, the amount of electricity stored in mobile devices is still finite, while the power consumption tends to increase as the screen size increases. An image display device including a color filter influences the design and performance of the mobile terminal because it is directly linked to the usable time and charging frequency of the mobile terminal.

Here, the color filter is generally formed on a transparent substrate, a colored layer formed on the transparent substrate and composed of colored patterns of the three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. It has a formed light-shielding portion.
In such a method for forming a colored layer, a pigment dispersion method using a pigment having excellent heat resistance and light resistance as a coloring material has been widely used. However, it has become difficult for color filters using pigments to meet the current demand for higher brightness.

As one means for achieving high brightness, a colored resin composition using a dye has been studied. Dyes generally have higher transmittance than pigments and can produce high-brightness color filters, but they have poor heat resistance and light resistance, and the chromaticity is likely to change during high-temperature heating in the color filter manufacturing process. There was a problem. Further, the colored resin composition using a dye has a problem that the solvent resistance of the cured coating film is poor and the dye is transferred to an adjacent cured film that does not contain a colorant such as pixels of other colors or a protective film. .. Further, the colored resin composition used by dissolving the dye is used as a color filter because of the problem that foreign substances are easily deposited on the surface of the cured coating film in the drying step and the contrast is remarkably lowered by the fluorescence emission of the dye. Had many problems.

As a method for improving various resistances of dyes, a method for producing salts of dyes is known. However, even if the dye is salt-formed, in the conventional colored resin composition, the salt-forming colorant of the dye fades due to the high-temperature heating performed at the time of forming the colored layer, and the brightness of the colored layer actually decreases. Therefore, it was still difficult to achieve high brightness. In Patent Document 1, the applicant applies to a color filter or the like using a salt-forming material of a specific dye containing a divalent or higher cation in which a plurality of dye skeletons are crosslinked by a cross-linking group and a divalent or higher anion. Is disclosed. According to the salt-forming color material of the above dye, it is disclosed that a molecular aggregate is formed by containing a divalent or higher cation and a divalent or higher anion, and heat resistance and solvent resistance are improved.
However, the heat resistance of the colored resin composition containing the salt-forming colorant of the dye for suppressing fading due to high-temperature heating performed at the time of forming the colored layer and achieving high brightness is required to be further improved. Has been done.

On the other hand, in the colored resin composition for a color filter, improvement of developability and formation of a high-definition pattern have been attempted by using a resin that expresses a polar group in a side chain by the action of an acid (Patent Documents). 2-5).
Further, Patent Document 6 describes a coloring composition containing a pigment and a resin obtained by copolymerizing a specific polymerizable monomer such as butyl (meth) acrylate with another polymerizable monomer. A coloring composition is disclosed in which the amount of a component derived from a polymerizable monomer is 56% by weight or more based on the total solid content of the resin, and the amount of a component derived from the specific polymerizable monomer is the total solid content of the resin. It is stated that when the content is 56% by weight or more in a minute, the effect of improving the light resistance can be obtained by sufficient interaction with the pigment.
Further, in Patent Document 7, in a pigment dispersion using a diketopyrrolopyrrole pigment, a cured film having excellent heat resistance and excellent contrast is formed so as to hinder the crystal growth of the diketopyrrolopyrrole pigment during heating. The weight of the main chain and the side chain in the graft polymer is composed of a graft polymer containing a structural unit having an amide group in the main chain and a structural unit derived from t-butyl methacrylate in the side chain. A pigment dispersant having a specific ratio and a pigment dispersion containing a specific organic solvent are disclosed.
Further, Patent Document 8 discloses a non-aqueous dispersant having a phosphonate ester group as an affinity site of particles capable of forming a resin layer having excellent dispersibility and excellent alkali resistance by the present applicant. There is.

International Publication No. 2012/144521 Japanese Unexamined Patent Publication No. 10-160924 Japanese Unexamined Patent Publication No. 10-260532 Japanese Unexamined Patent Publication No. 2000-221682 Japanese Unexamined Patent Publication No. 2014-170189 Japanese Unexamined Patent Publication No. 2013-160817 Japanese Unexamined Patent Publication No. 2013-125087 Japanese Unexamined Patent Publication No. 2015-107471

In the conventional colored resin composition, the chromaticity is changed by high-temperature heating performed at the time of forming the colored layer, and the brightness of the colored layer may be lowered. Further, in a color filter, it is required to prepare a colored layer with a thinner film thickness.

The embodiment of the present disclosure has been made in view of the above problems, and is a polymer dispersant capable of suppressing a change in chromaticity after high-temperature heating, improving brightness, and forming a thinner colored layer. The color material dispersion liquid, which contains the polymer dispersant, suppresses chromaticity change after high-temperature heating, improves brightness, and can form a thinner colored layer, and contains the color material dispersion liquid. A colored resin composition capable of suppressing a change in chromaticity after high-temperature heating, improving brightness, and forming a thinner colored layer, a color filter formed by using the colored resin composition, and the color filter. It is an object of the present invention to provide a liquid crystal display device and a light emitting display device having the above.

One embodiment of the present disclosure is a copolymer having at least one selected from the structural unit represented by the following general formula (I) and the structural unit represented by the following general formula (I') at 230 ° C. Before and after heating for 5 minutes or more, the peak intensity derived from at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group decreases and the peak intensity derived from the acid anhydride group increases in the infrared absorption spectrum. Provided is a polymer dispersant.

（一般式（Ｉ）及び一般式（Ｉ’）中、Ｌ^１は、直接結合又は２価の連結基、Ｒ^１は、水素原子又はメチル基、Ｒ^２は、炭化水素基、−［ＣＨ（Ｒ^３）−ＣＨ（Ｒ^４）−Ｏ］_ｘ１−Ｒ^５、又は−［（ＣＨ_２）_ｙ１−Ｏ］_ｚ１−Ｒ^５で示される１価の基、Ｒ^３及びＲ^４は、それぞれ独立に水素原子又はメチル基、Ｒ^５は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^６で示される１価の基であり、Ｒ^６は水素原子又は炭素数１〜５のアルキル基であり、前記炭化水素基は置換基を有していてもよい。ｘ１は１以上１８以下の整数、ｙ１は１以上５以下の整数、ｚ１は１以上１８以下の整数を表す。
一般式（Ｉ’）中、Ｘ^＋は有機カチオンを表す。）

(In the general formula (I) and the general formula (I'), L ¹ is a direct bond or a divalent linking group, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group, and-[CH ( R ³ ) -CH (R ⁴ ) -O] _x1- R ⁵ or-[(CH ₂ ) _y1- O] _z1- R ^{5 The} monovalent groups, R ³ and R ⁴ , are independent of each other. Hydrogen atom or methyl group, R ⁵ is hydrogen atom, hydrocarbon group, -CHO, -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ⁶ It is a monovalent group represented by, R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have a substituent. X1 is an integer of 1 or more and 18 or less. , Y1 represents an integer of 1 or more and 5 or less, and z1 represents an integer of 1 or more and 18 or less.
In the general formula (I'), X ⁺ represents an organic cation. )

In one embodiment of the present disclosure, at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and the following general formula (II) are shown. It is a block copolymer having the structural unit to be formed, or at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and the following general. Provided is a polymer dispersant, which is a graft copolymer having a structural unit represented by the formula (III).

（一般式（ＩＩ）中、Ｒ^７は水素原子又はメチル基を表し、Ｒ^Ｐは下記一般式（Ａ）で表される１価の保護基を表す。
一般式（ＩＩＩ）中、Ｒ^８は水素原子又はメチル基、Ｌ^２は直接結合又は２価の連結基を表し、Ｐｏｌｙｍｅｒは、下記一般式（ＩＶ）で表される構成単位を有するポリマー鎖を表す。）

(In the general formula (II), R ⁷ represents a hydrogen atom or a methyl group, R ^P represents a monovalent protective group represented by the following general formula (A).
In the general formula (III), R ⁸ represents a hydrogen atom or a methyl group, L ² represents a direct bond or a divalent linking group, and Polymer represents a polymer chain having a structural unit represented by the following general formula (IV). show. )

（一般式（Ａ）中、Ｒ^Ｐ１は、炭素原子又はケイ素原子を表し、Ｒ^Ｐ２、Ｒ^Ｐ３及びＲ^Ｐ４はそれぞれ独立に、水素原子又は炭化水素基を表し、Ｒ^Ｐ５は、炭化水素基又は−ＯＲ^Ｐ６を表し、Ｒ^Ｐ６は炭化水素基を表す。Ｒ^Ｐ４及びＲ^Ｐ５は互いに結合して環構造を形成してもよい。）

(In the general formula ^{(A), R P1} represents a carbon atom or a silicon ^atom, R ^{P2, R P3} and ^{R P4} each independently represent a hydrogen atom or a hydrocarbon ^{group, R P5} is a hydrocarbon group or represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)

（一般式（ＩＶ）中、Ｒ^９は水素原子又はメチル基を表し、Ｒ^Ｐ’は下記一般式（Ａ’）で表される１価の保護基を表す。ｎは５以上２００以下の整数を表す。）

(In the general formula (IV), R ⁹ is a hydrogen atom or a methyl group, R P ^'is the following general formula (A' .n representing a monovalent protecting group represented by) 5 to 200 integer Represents.)

（一般式（Ａ’）中、Ｒ^Ｐ’１は、炭素原子又はケイ素原子を表し、Ｒ^Ｐ’２、Ｒ^Ｐ’３及びＲ^Ｐ’４はそれぞれ独立に、水素原子又は炭化水素基を表し、Ｒ^Ｐ’５は、炭化水素基又は−ＯＲ^Ｐ’６を表し、Ｒ^Ｐ’６は炭化水素基を表す。Ｒ^Ｐ’４及びＲ^Ｐ’５は互いに結合して環構造を形成してもよい。）

(In the general formula (A '), ^{R P'1} represents a carbon atom or a silicon atom, ^{R P'2, R P'3} and ^{R P'4} each independently represent a hydrogen atom or a hydrocarbon group , ^{R P'5} represents a hydrocarbon group or -OR ^{P'6, R P'6} is .R ^P'4 and ^{R P'5} represents a hydrocarbon group bonded to form a ring system with one another May be good.)

In one embodiment of the present disclosure, the copolymer further comprises an —O— bond derived from a monomer having a glass transition temperature value (Tgi) of less than 50 ° C. in the homopolymer. Provided is a polymer dispersant having a structural unit containing a good hydrocarbon group in a side chain.

In one embodiment of the present disclosure, the copolymer further comprises a hydrocarbon group in the side chain, which is derived from a monomer having a glass transition temperature value (Tgi) of 50 ° C. or higher in the homopolymer. Provided is a polymer dispersant having a structural unit.

One embodiment of the present disclosure contains (A) a coloring material, (B) a dispersant, and (C) a solvent, and the (B) dispersant contains the above-mentioned polymer dispersant. A material dispersion is provided.

In one embodiment of the present disclosure, the color material (A) provides a color material dispersion liquid, which is a metal lake color material of a dye.

One embodiment of the present disclosure provides a colored resin composition containing the above-mentioned coloring material dispersion, (D) alkali-soluble resin, (E) polyfunctional monomer, and (F) photoinitiator. ..

In one embodiment of the present disclosure, a colored resin composition is provided in which the polyfunctional monomer (E) contains a phosphorus atom-containing polyfunctional monomer.

One embodiment of the present disclosure is a color filter including at least a transparent substrate and a colored layer on the transparent substrate, wherein at least one of the colored layers is a cured product of the colored resin composition described above. Provide a filter.

One embodiment of the present disclosure provides a liquid crystal display device having the above-mentioned color filter, a facing substrate, and a liquid crystal layer located between the color filter and the facing substrate.

One embodiment of the present disclosure provides a light emitting display device having the above-mentioned color filter and a light emitting body.

One embodiment of the present disclosure is the method for producing the polymer dispersant, which is a structural unit having one or more reactive groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group. Provided is a method for producing a polymer dispersant, which comprises a step of reacting an organic phosphonic acid with the reactive group of the copolymer having.

In one embodiment of the present disclosure, as one embodiment of the method for producing a polymer dispersant, the structural unit represented by the general formula (II), a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group are used. A step of reacting an organic phosphonic acid with the reactive group of a block copolymer having a structural unit having one or more reactive groups selected from the group consisting of
A graft having a structural unit represented by the general formula (III) and a structural unit having one or more reactive groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group. Provided is a method for producing a polymer dispersant, which comprises any of the steps of reacting an organic phosphonic acid with the reactive group of the polymer.

The embodiment of the present disclosure contains a polymer dispersant and the polymer dispersant capable of suppressing a change in chromaticity after high-temperature heating, improving brightness, and forming a thinner colored layer, and high-temperature heating. The subsequent chromaticity change is suppressed, the brightness is improved, and the color material dispersion liquid capable of forming a thinner colored layer and the color material dispersion liquid are contained, and the chromaticity change after high temperature heating is suppressed. Provided are a colored resin composition having improved brightness and capable of forming a thinner colored layer, a color filter formed by using the colored resin composition, and a liquid crystal display device and a light emitting display device having the color filter. can do.

It is a schematic cross-sectional view which shows an example of the color filter of this disclosure. It is the schematic sectional drawing which shows an example of the liquid crystal display device of this disclosure. It is the schematic sectional drawing which shows an example of the light emission display device of this disclosure. It is an infrared absorption spectrum before and after post-baking of the polymer dispersant D obtained in Example 4. It is a partially enlarged view of the infrared absorption spectrum before and after post-baking of the polymer dispersant D obtained in Example 4. It is an infrared absorption spectrum before and after post-baking of the comparative polymer dispersant E obtained in Comparative Example 1. It is a partially enlarged view of the infrared absorption spectrum before and after post-baking of the comparative polymer dispersant E obtained in Comparative Example 1.

Hereinafter, the polymer dispersant and its production method, the coloring material dispersion, the colored resin composition, the color filter, the liquid crystal display device, and the light emitting display device according to the present disclosure will be described in order.
In the present specification, (meth) acrylic represents each of acrylic and methacrylic, (meth) acrylate represents each of acrylate and methacrylate, and (meth) acryloyl represents each of acryloyl and methacrylic. ..
Further, in the present specification, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

1. 1. Polymer Dispersant The polymer dispersant of the present disclosure is a polymer having at least one selected from the structural unit represented by the following general formula (I) and the structural unit represented by the following general formula (I'). Yes, before and after heating at 230 ° C. for 5 minutes or more, the peak intensity derived from at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group decreased in the infrared absorption spectrum, and the peak derived from the acid anhydride group decreased. A polymer dispersant with increased strength.

（一般式（Ｉ）及び一般式（Ｉ’）中、Ｌ^１は、直接結合又は２価の連結基、Ｒ^１は、水素原子又はメチル基、Ｒ^２は、炭化水素基、−［ＣＨ（Ｒ^３）−ＣＨ（Ｒ^４）−Ｏ］_ｘ１−Ｒ^５、又は−［（ＣＨ_２）_ｙ１−Ｏ］_ｚ１−Ｒ^５で示される１価の基、Ｒ^３及びＲ^４は、それぞれ独立に水素原子又はメチル基、Ｒ^５は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、−ＣＯ−ＣＨ＝ＣＨ_２、−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２又は−ＣＨ_２ＣＯＯＲ^６で示される１価の基であり、Ｒ^６は水素原子又は炭素数１〜５のアルキル基であり、前記炭化水素基は置換基を有していてもよい。ｘ１は１以上１８以下の整数、ｙ１は１以上５以下の整数、ｚ１は１以上１８以下の整数を表す。
一般式（Ｉ’）中、Ｘ^＋は有機カチオンを表す。）

(In the general formula (I) and the general formula (I'), L ¹ is a direct bond or a divalent linking group, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group, and-[CH ( R ³ ) -CH (R ⁴ ) -O] _x1- R ⁵ or-[(CH ₂ ) _y1- O] _z1- R ^{5 The} monovalent groups, R ³ and R ⁴ , are independent of each other. Hydrogen atom or methyl group, R ⁵ is hydrogen atom, hydrocarbon group, -CHO, -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ⁶ It is a monovalent group represented by, R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have a substituent. X1 is an integer of 1 or more and 18 or less. , Y1 represents an integer of 1 or more and 5 or less, and z1 represents an integer of 1 or more and 18 or less.
In the general formula (I'), X ⁺ represents an organic cation. )

The infrared absorption spectrum of the polymer dispersant according to the present disclosure is based on the coating film formed by applying a dispersant solution prepared by dissolving the polymer dispersant according to the present disclosure in a solvent and drying the coating film. Obtained by measuring the infrared absorption spectrum.
The solvent used in the dispersant solution can be appropriately selected from those capable of dissolving the polymer dispersant according to the present disclosure and being dried and removed by heating at less than 150 ° C., and is not particularly limited, but for example, propylene glycol monomethyl. Examples thereof include ether acetate and propylene glycol monomethyl ether.
The solid content concentration of the dispersant solution, that is, the concentration of the polymer dispersant according to the present disclosure is not particularly limited, but is usually about 10% by mass or more and 30% by mass or less. The thickness of the coating film after heating at 230 ° C. is not particularly limited, but is about 2.0 μm ± 0.5 μm.
The heating time at 230 ° C. is not particularly limited as long as it is 5 minutes or more, but is usually 10 minutes or more and 120 minutes or less.

Further, in the infrared absorption spectrum of the polymer dispersant according to the present disclosure, the peak derived from the methylene group of the main chain is set as a reference peak, and the peak intensity of the reference peak is set to 1. As the reference peak derived from the methylene group of the main chain, the peak having the maximum value among the peaks in which the inflection point is observed at ^{1450 ± 10 cm -1 can be mentioned.}
In the infrared absorption spectrum of the polymer dispersant according to the present disclosure, as the peak derived from the acid anhydride group, for example, the peak having the maximum value among the peaks in which an inflection point is observed at ^{1760 ± 5 cm -1 is used.} Can be mentioned.
In the polymer dispersant according to the present disclosure, in the infrared absorption spectrum after heating, the peak intensity of the peak having the maximum value at ^{1760 ± 5 cm -1 is preferably 0.35 or more, preferably 0.7 or more.} Is more preferable.
Further, in the infrared absorption spectrum of the polymer dispersant according to the present disclosure, as a peak derived from at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group, for example, a distorted point is observed near ^{2980 cm -1.} The peak having the maximum value among the peaks to be formed can be mentioned.

The polymer dispersant according to the present disclosure has an effect of improving the heat resistance of the colored layer using the color material dispersion liquid even when a color material having low heat resistance such as a rake color material is dispersed, and has a post. Since fading of the coloring material can be suppressed even under high-temperature heating such as baking, a high-brightness colored layer can be formed. Further, by using the polymer dispersant according to the present disclosure, the colored layer can be further thinned.

The action of the polymer dispersant according to the present disclosure to exert the above effects is presumed as follows.
The polymer dispersant according to the present disclosure has an acidic phosphorus compound group (-P) having at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the following general formula (I'). (= O) (-R ² ) (OH)) and its salt (-P (= O) (-R ² ) (O ^- X ⁺ )) are easily adsorbed on the coloring material, so that the dispersibility of the coloring material And the dispersion stability can be made excellent. Further, in the polymer dispersant according to the present disclosure, the peak intensity derived from at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group decreases in the infrared absorption spectrum before and after heating at 230 ° C. for 5 minutes or more. However, since the peak intensity derived from the acid anhydride group increases, the carboxy group appears by desorbing the protective group containing at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group by the heating. Further, an acid anhydride group appears by dehydration condensation of adjacent carboxy groups. The polymer dispersant of the present disclosure has at least one hydrocarbon group and a hydrocarbon group-substituted silyl group at the time of dispersion, has high solvent solubility and good dispersibility, while forming a colored layer. After post-baking, the protective group containing at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group is eliminated and a carboxy group and an acid anhydride group appear to form a skeleton having a high glass transition temperature (Tg). It is considered that the heat resistance is improved. Further, the polymer dispersant of the present disclosure is excellent in heat resistance in the vicinity of the coloring material because the acidic phosphorus compound group is easily adsorbed on the coloring material and therefore tends to be present in the vicinity of the coloring material in the coloring layer. It is presumed that the skeleton exists. As a result, the molecular motion of the coloring material due to heating is suppressed, and the fading of the coloring material is suppressed. Therefore, it is considered that the decrease in the brightness of the coloring layer is suppressed and a high-brightness coloring layer can be formed.
Further, in the colored layer formed by using the polymer dispersant according to the present disclosure, a protective group containing at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group desorbed after post-baking is contained in the colored layer. By removing the carboxy groups and dehydrating and condensing the adjacent carboxy groups, the colored layer can be made thinner while increasing the concentration of the coloring material in the colored layer.

Further, the polymer dispersant according to the present disclosure uses a coloring material having low heat resistance such as a rake coloring material as compared with the case where the coloring material affinity site is another acidic group such as a basic group or a carboxy group. When dispersed, it is highly effective in suppressing fading of the coloring material. This is because at least one of the acidic phosphorus compound group and its salt is attached to the surface of the rake color material, so that active oxygen such as peroxy radicals attacks the pigment skeleton of the rake color material (hydrogen extraction). ) Is suppressed, and it is presumed that the deterioration of the coloring material (oxidative deterioration) is suppressed.

At least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') has a structural unit obtained by polymerizing an ethylenically unsaturated monomer. The copolymer, which is the polymer dispersant according to the present disclosure, is an ethylenically unsaturated monomer copolymer copolymerized with another ethylenically unsaturated monomer.

<Constituent unit represented by the general formula (I) and the structural unit represented by the general formula (I')>
In the general formula (I) and the general formula (I'), L ¹ is a direct bond or a divalent linking group. The direct bond means that the phosphorus atom in the side chain is directly bonded to the carbon atom of the main chain skeleton without interposing a linking group.
The ^{divalent linking group in L 1} is not particularly limited as long as the carbon atom of the main clavicle and the phosphorus atom can be linked. Examples of the divalent linking group in L ¹ include a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, a -CONH- group, and a -COO- group. Examples thereof include -NHCOO- group, ether group (-O- group), thioether group (-S- group), and a combination thereof. In the present invention, the direction of bonding of the divalent linking group is arbitrary. That is, when -CONH- is contained in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the phosphorus atom side of the side chain, and conversely, -NH may be on the main chain. -CO may be on the phosphorus atom side of the side chain on the carbon atom side of the side chain.

^{Among them, from the viewpoint of dispersibility, L 1} in the general formula (I) and the general formula (I') is preferably a -CONH- group or a divalent linking group containing a -COO- group.
For example, when L ¹ is a divalent linking group containing a -COO- group, the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') are each represented by the following formula (I). Examples thereof include a structure represented by -1) and a structure represented by the following formula (I'-1).

（一般式（Ｉ−１）及び一般式（Ｉ’−１）中、Ｒ^１、及びＲ^２は、一般式（Ｉ）及び一般式（Ｉ’）と同様であり、Ｘ^＋は、一般式（Ｉ’）と同様であり、Ｌ^１’は、水酸基を有していても良い炭素数が１個以上８個以下のアルキレン基、−［ＣＨ（Ｒ^ａ）−ＣＨ（Ｒ^ｂ）−Ｏ］_ｘ−、又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−Ｏ−、−［ＣＨ（Ｒ^ｃ）］_ｗ−Ｏ−、であり、Ｒ^ａ、Ｒ^ｂ及びＲ^ｃは、それぞれ独立に水素原子、メチル基、又は水酸基である。Ｒ^ａ、Ｒ^ｂ及びＲ^ｃが複数ある場合は、各々同一であっても異なっていても良い。ｘは１以上１８以下の整数、ｙは１以上５以下の整数、ｚは１以上１８以下の整数、ｗは１以上１８以下の整数を表す。）

(In the general formula (I-1) and the general formula (I'-1), R ¹ and R ² are the same as the general formula (I) and the general formula (I'), and X ⁺ is the general formula. (I ') is the same as, ^{L 1'} is carbon atoms, which may have a hydroxyl group one or more than eight alkylene ^{group, - [CH (R a)} -CH (R b) -O ] _X − or − [(CH ₂ ) _y − O] _z − (CH ₂ ) _y − O −, − [CH (R ^c )] _w ^{− O −, and Ra} , R ^b, and R ^c. Are independently hydrogen atoms, methyl groups, or hydroxyl groups. When there are ^a plurality of R a, R ^b, and R ^c , they may be the same or different. X is an integer of 1 or more and 18 or less. , Y is an integer of 1 or more and 5 or less, z is an atom of 1 or more and 18 or less, and w is an integer of 1 or more and 18 or less.)

Alkylene group 8 or less 1 or more carbon atoms in L 1 ^'is a straight-chain, branched, or or cyclic, for example, methylene group, ethylene group, trimethylene group, propylene group, various It is a butylene group, various pentylene groups, various hexylene groups, various octylene groups, etc., and a part of hydrogen may be substituted with a hydroxyl group.
x is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less, and y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably. Is 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, and more preferably an integer of 1 or more and 2 or less. w is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less.

^{Suitable specific examples of L 1 in} the general formula (I) and the general formula (I') include, for example, -COO-CH ₂ CH (OH) CH ₂ -O-, -COO-CH ₂ CH _2- O-. CH ₂ CH (OH) CH ₂ −O−, −COO−CH ₂ C (CH ₂ CH ₃ ) (CH ₂ OH) CH ₂ −O− and the like can be mentioned, but the present invention is not limited thereto.

As the hydrocarbon group for R ^2, for example, 1 or more 18 or less alkyl group with a carbon number, more than 18 or less alkenyl carbon atoms, an aralkyl group, and an aryl group.
The alkyl group having 1 or more and 18 or less carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or n-butyl. Examples thereof include a group, a cyclopentyl group, a cyclohexyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, a lower alkyl group substituted adamantyl group and the like.
The alkenyl group having 2 or more and 18 or less carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group and the like. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond is at the end of the alkenyl group.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xsilyl group and the like, and may further have a substituent. The aryl group preferably has 6 or more and 24 or less carbon atoms, and more preferably 6 or more and 12 or less carbon atoms.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The number of carbon atoms of the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include a halogen atom such as F, Cl and Br, a nitro group and the like.
Further, as the substituent of the aromatic ring such as the aryl group or the aralkyl group, a linear or branched alkyl group having 1 or more and 4 or less carbon atoms, an alkenyl group, a nitro group, a halogen atom and the like can be used. Can be mentioned.
The preferable carbon number does not include the carbon number of the substituent.
In the ^{R 2,} x1 is said x, y1 is said y, z1 are as defined above z.
Examples of the hydrocarbon group in R ⁵ include the same hydrocarbon groups as in R ² .

As the structural unit represented by the general formula (I), R ² in the general formula (I) may have a methyl group, an ethyl group, a substituent, an aryl group or an aralkyl group, a vinyl group, and the like. Allyl group,-[CH (R ³ ) -CH (R ⁴ ) -O] _x1- R ⁵ , or-[(CH ₂ ) _y1- O] _z1- R ⁵ monovalent group, R ³ and R ⁴ is an independently hydrogen atom or a methyl group, and the dispersibility and dispersion of particles ^{in which R 5} is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH _{2 are dispersed.} It is preferable because it has excellent stability. Of these, an aryl group which may have a substituent is more preferable from the viewpoint of dispersibility.
The structural unit represented by the general formula (I) may be contained alone or in combination of two or more in the polymer.

Further, in the general formula (I'), X ⁺ represents an organic cation. An organic cation means one containing a carbon atom in a cation portion. Examples of the organic cation include ammonium cations such as imidazolium cation, pyridinium cation, aminidium cation, piperidinium cation, pyrrolidinium cation, tetraalkylammonium cation and trialkylammonium cation, and sulfonium cation such as trialkylsulfonium cation. , A phosphonium cation such as a tetraalkylphosphonium cation, and the like. Of these, a protonated nitrogen-containing organic cation is preferable from the viewpoint of dispersibility and alkali developability.
Above all, when the organic cation has an ethylenically unsaturated double bond, it is preferable because it can impart curability.

As the structural unit represented by the general formula (I'), R ² in the general formula (I') may have a methyl group, an ethyl group, a substituent, an aryl group or an aralkyl group, and vinyl. Group, allyl group, -[CH (R ³ ) -CH (R ⁴ ) -O] _x1- R ⁵ or-[(CH ₂ ) _y1- O] _z1- R ⁵ monovalent group, R ³ and R ⁴ are independently hydrogen atoms or methyl groups, R ⁵ is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , and X ⁺ is protonated. Nitrogen organic cations, especially those that are protonated imidazolium cations, are preferable from the viewpoint of excellent dispersibility, dispersion stability and alkali developability of the dispersed particles, and among them, R ² has a substituent. A good aryl group is more preferable from the viewpoint of dispersibility.
The structural unit represented by the general formula (I') may be contained alone or in combination of two or more in the polymer.

The polymer dispersant of the present disclosure may contain both structural units represented by the general formula (I) and the structural unit represented by the general formula (I'). When both of the constituent units are included, it is sufficient as long as good dispersibility and dispersion stability are ensured, and there is no particular limitation, but the ratio of the number of constituent units represented by the general formula (I') is , The total number of structural units represented by the general formula (I) and the general formula (I') is preferably 0 to 50 mol%.

Further, in the polymer dispersant of the present disclosure, at least one content ratio selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') is dispersibility and From the viewpoint of dispersion stability, when all the constituent units are 100% by mass, it is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 55% by mass or less, and 25% by mass. More preferably, it is% or more and 52% by mass or less.
In the present disclosure, the content ratio (mass%) of the constituent units is calculated from the amount charged when synthesizing the copolymer.

<Thermal potential building block>
The polymer dispersant according to the present disclosure further reduces the peak intensity derived from at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group in the infrared absorption spectrum before and after heating at 230 ° C. for 5 minutes or more. However, it has a structure in which the peak intensity derived from the acid anhydride group is increased. In such a structure, two or more thermally latent building blocks derived from an ethylenically unsaturated monomer, which contain a carboxy group protected by a hydrocarbon group or a hydrocarbon group-substituted silyl group in the side chain, are located adjacent to each other. The structure is preferable.
When two or more of the thermal latent building units are located adjacent to each other, the heating causes desorption of the protecting group containing at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group to form a carboxy group, which becomes a carboxy group. Acid anhydride groups are formed by dehydration condensation of carboxy groups from adjacent thermal latent building blocks.
Examples of the protecting group containing at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group by the heating include a structure derived from a vinyl ether compound containing a hydrocarbon group, a hydrocarbon group-substituted silyl group and a hydrocarbon group. Be done.
As the thermal latent structural unit, a structural unit represented by the following general formula (II) is preferable.

（一般式（ＩＩ）中、Ｒ^７は水素原子又はメチル基を表し、Ｒ^Ｐは下記一般式（Ａ）で表される１価の保護基を表す。）

(In the general formula (II), R ⁷ represents a hydrogen atom or a methyl group, R ^P represents a monovalent protective group represented by the following general formula (A).)

（一般式（Ａ）中、Ｒ^Ｐ１は、炭素原子又はケイ素原子を表し、Ｒ^Ｐ２、Ｒ^Ｐ３及びＲ^Ｐ４はそれぞれ独立に、水素原子又は炭化水素基を表し、Ｒ^Ｐ５は、炭化水素基又は−ＯＲ^Ｐ６を表し、Ｒ^Ｐ６は炭化水素基を表す。Ｒ^Ｐ４及びＲ^Ｐ５は互いに結合して環構造を形成してもよい。）

(In the general formula ^{(A), R P1} represents a carbon atom or a silicon ^atom, R ^{P2, R P3} and ^{R P4} each independently represent a hydrogen atom or a hydrocarbon ^{group, R P5} is a hydrocarbon group or represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)

R ^P1 of the general formula (A) are, inter alia that a carbon atom is versatile and preferable from the viewpoint of the stability of the protecting group itself.
As the hydrocarbon group for ^{R P2, R P3, R P4} , R P5 , and ^{R P6} in the general formula (A), it is an aliphatic hydrocarbon group may be an aromatic hydrocarbon group, particularly limited Although not, it is preferably an aliphatic hydrocarbon group, and among them, linear, branched, cyclic and combination alkyl groups thereof are preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-hexyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. Cyclohexylmethyl group and the like can be mentioned.
Among them, R ^P2 and R ^P3 of the general formula (A) are each independently preferably a hydrogen atom or a C 1 to 3 alkyl group carbon, and more preferably a hydrogen atom. In ^RP2 and ^RP3 , as the alkyl group having 1 or more and 3 or less carbon atoms, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
R ^P4 of the general formula (A), 1 to 3 carbon atoms an alkyl group, or that forms a ring structure with R ^P5 is preferably, 1 to 3 of alkyl group having a carbon number Is more preferable. In ^RP4 , as the alkyl group having 1 or more and 3 or less carbon atoms, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
^{R P5} of the general formula (A), form a ring structure having one or more carbon atoms of 3 or less alkyl group, and the ^{R P6} is 1 to 18 alkyl group carbon atoms in ^{-OR P6,} or the ^{R P4} It is preferable that the alkyl group has 1 or more carbon atoms and 3 or less carbon atoms. In ^RP5 , as the alkyl group having 1 or more and 3 or less carbon atoms, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable. R ^P6 is more preferably an alkyl group having 3 or more carbon atoms and 10 or less carbon atoms.
The R ^P4 and ^{R P5} are bonded together to form a ring ^structure, means ^{that R P4} and ^{R P5} form a ring structure through an ^{R P1.} When ^RP1 is a carbon atom ^{, examples of the ring structure formed by bonding RP4} and ^RP5 to each other include cycloalkane and adamantane having 3 or more and 6 or less carbon atoms. When ^RP1 is a silicon atom, for example, ^{a heterocycle in which a carbon atom located at RP1} in the ring structure described above is replaced with a silicon atom can be mentioned.

Specific examples of the monovalent protecting group represented by the general formula (A) include a t-butyl group, a sec-butyl group, a trimethylsilyl group, a 2-methyl-2-adamantyl group, and the following general formula ( Examples thereof include a structure derived from the vinyl ether compound represented by A-1).

（一般式（Ａ−１）中、Ｒ^Ｐ６は炭化水素基を表す。）

(In the general formula (A-1), ^RP6 represents a hydrocarbon group.)

^{Examples of the hydrocarbon group in RP6} in the general formula (A-1) ^{include those similar to the hydrocarbon group in RP6} in the general formula (A), and among them, an alkyl having 1 or more and 18 or less carbon atoms. A group is preferable, and an alkyl group having 3 or more and 10 or less carbon atoms is more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, cyclohexylmethyl group and the like. Of these, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, n-hexyl group and cyclohexyl group are preferable, and methyl group, ethyl group, propyl group and isopropyl group are preferable from the viewpoint of solvent solubility. The n-butyl group is more preferable.

Structural unit represented by the general formula (II), by heating 5 minutes or more at 230 ° C., will carboxy group R ^P is eliminated, the two structural units represented by the general formula (II) By being positioned adjacent to each other as described above, the carboxy groups of the constituent units located adjacent to each other are dehydrated and condensed to form an acid anhydride group, and the structure represented by the following general formula (II-a) is formed. Become.

（一般式（ＩＩ−ａ）中、Ｒ^７は一般式（ＩＩ）と同様である。複数あるＲ^７は同一であっても異なっていてもよい。）

(In the general formula (II-a), R ⁷ is the same as the general formula (II). A plurality of R ^7s may be the same or different.)

In the polymer dispersant of the present disclosure, the content ratio of the thermal latent structural unit is 5 from the viewpoint of heat resistance and brightness and the thinning of the colored layer when all the structural units are 100% by mass. It is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 80% by mass or less from the viewpoint of dispersibility, 75% by mass. It is more preferably mass% or less, and even more preferably 70 mass% or less.

<Low Tg constituent unit>
The polymer dispersant according to the present disclosure may further contain an —O— bond derived from a monomer having a glass transition temperature value (Tgi) of less than 50 ° C. in the homopolymer. Having a structural unit containing a group in the side chain (referred to as “low Tg structural unit” in the present specification) can improve the solvent solubility of the polymer dispersant and the solvent resolubility of the solid content of the colored resin composition. It is preferable from the point of view. Further, in the low Tg constituent unit, the value of the glass transition temperature (Tgi) is not particularly limited, but is preferably −100 ° C. or higher from the viewpoint of ensuring the durability of the dispersant itself. , -50 ° C or higher is preferable.
As the glass transition temperature value (Tgi) of the monomeric homopolymer, the value of Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
Examples of the low Tg structural unit include a structural unit represented by the following general formula (V).

（一般式（Ｖ）中、Ｒ^１０は水素原子又はメチル基、Ｌ^３は直接結合又は２価の連結基、Ｒ^１１は、−Ｏ−結合を含んでいてもよい炭化水素基を表す。）

(In the general formula (V), R ¹⁰ represents a hydrogen atom or a methyl group, L ³ represents a direct bond or a divalent linking group, and R ¹¹ represents a hydrocarbon group which may contain an —O— bond.)

In the general formula (V), the ^{divalent linking group in L 3} is the same as in ^{L 1 of the} general formula (I). When L ³ is directly bonded, it means that R ¹¹ is directly bonded to a carbon atom without interposing a linking group. Above all, from the viewpoint of dispersibility, L ³ in the general formula (V) is preferably a divalent linking group containing a −COO− group.
^{Examples of the hydrocarbon group which may contain an —O— bond in R 11} of the general formula (V) include a linear or branched hydrocarbon group having 4 to 10 carbon atoms which may contain an —O— bond. Alkane group,-(CH _2- CH _2- O) _n- R ¹² (R ¹² represents a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, and n is an integer of 2 or more and 10 or less. The group represented by) is preferable, and a linear or branched alkyl group having 4 to 10 carbon atoms is more preferable.

Specific examples of the monomer for inducing the structural unit represented by the general formula (V) include n-butyl methacrylate (Tgi: 20 ° C.), isobutyl methacrylate (Tgi: 48 ° C.), and 2-ethylhexyl. Examples thereof include methacrylate (Tgi: −10 ° C.), 2-ethoxyethyl methacrylate (Tgi: -16 ° C.), isodecyl methacrylate (Tgi: −41 ° C.), methoxypolyethylene glycol # 400 methacrylate (Tgi: −69 ° C.), and the like. Of these, n-butyl methacrylate, 2-ethylhexyl methacrylate, and 2-ethoxyethyl methacrylate are preferable from the viewpoint of the durability of the dispersant.

In the polymer dispersant of the present disclosure, the content ratio of the low Tg structural unit is preferably 10% by mass or more, preferably 15% by mass, from the viewpoint of solvent solubility when all the structural units are 100% by mass. % Or more, while it is preferably 60% by mass or less, and more preferably 50% by mass or less from the viewpoint of substrate adhesion of the colored layer.

<High Tg constituent unit>
The polymer dispersant according to the present disclosure is a hydrocarbon having the low Tg constituent unit and further derived from a monomer having a glass transition temperature value (Tgi) of 50 ° C. or higher in the homopolymer. It is preferable to have a combination of structural units containing a group in the side chain (referred to as “high Tg structural unit” in the present specification) from the viewpoint of the strength and solvent resistance of the colored film.
Examples of the high Tg structural unit include a structural unit represented by the following general formula (VI).

（一般式（ＶＩ）中、Ｒ^１３は水素原子又はメチル基、Ｌ^４は直接結合又は２価の連結基、Ｒ^１４は炭化水素基を表す。）

(In the general formula (VI), R ¹³ represents a hydrogen atom or a methyl group, L ⁴ represents a direct bond or a divalent linking group, and R ¹⁴ represents a hydrocarbon group.)

In the general formula (VI), the ^{divalent linking group in L 4} is the same as in ^{L 1 of the} general formula (I). When L ⁴ is directly bonded, it means that R ¹⁴ is directly bonded to the carbon atom without interposing a linking group. Above all, from the viewpoint of dispersibility, L ⁴ in the general formula (VI) is preferably a divalent linking group containing a −COO− group.
Examples of the hydrocarbon group for R ¹⁴ of the general Formula (VI), among others, one or more carbon atoms of 3 or less linear or branched alkyl group, having 4 to 10 cycloaliphatic hydrocarbon group or cyclic carbon A combination of an aliphatic hydrocarbon group and an alkyl group, an aryl group having 6 or more and 10 or less carbon atoms, and an aralkyl group having 7 or more and 14 or less carbon atoms are preferable.
Examples of the linear or branched alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group and an i-propyl group.
Examples of the combination of the cyclic aliphatic hydrocarbon group having 4 or more and 10 or less carbon atoms or the cyclic aliphatic hydrocarbon group and the alkyl group include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and an alkyl such as a 1-methylcyclohexyl group. Examples thereof include a substituted cycloalkyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group and the like.
Examples of the aryl group having 6 or more and 10 or less carbon atoms include a phenyl group and a naphthyl group.
Examples of the aralkyl group having 7 or more and 14 or less carbon atoms include a benzyl group, an α-methylbenzyl group, an α, and an α-dimethylbenzyl group.

Specific examples of the monomer for inducing the structural unit represented by the general formula (VI) include methyl methacrylate (Tgi: 105 ° C), cyclohexyl methacrylate (Tgi: 66 ° C), and benzyl methacrylate (Tgi: Tgi:). 54 ° C.), isobonyl methacrylate (Tgi: 180 ° C.), adamantyl methacrylate (Tgi: 183 ° C.), etc. Among them, methyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate are preferable from the viewpoint of heat resistance and solvent solubility. ..

In the polymer dispersant of the present disclosure, the content ratio of the high Tg structural unit is preferably 5% by mass or more from the viewpoint of heat resistance and solvent resistance when all the structural units are 100% by mass. , 15% by mass or more, while it is preferably 60% by mass or less, and more preferably 50% by mass or less from the viewpoint of solvent solubility.

In the polymer dispersant of the present disclosure, the content ratio when both the low Tg constituent unit and the high Tg constituent unit are contained is when the total mass part of the low Tg constituent unit is 10 parts by mass. From the viewpoint of the solvent solubility of the polymer dispersant and the solvent resolubility of the solid content of the colored resin composition, the total mass part of the high Tg structural unit is preferably 35 parts by mass or less, preferably 30 parts by mass or less. More preferably, it is more preferably 25 parts by mass or less, and on the other hand, from the viewpoint of solvent resistance, the total mass part of the high Tg constituent unit is preferably 4 parts by mass or more, and 10 parts by mass or more. Is more preferable, and it is even more preferable that the amount is 15 parts by mass or more.

In the polymer dispersants of the present disclosure, among them, a low Tg constituent unit derived from at least one monomer selected from the group consisting of n-butyl methacrylate, 2-ethylhexyl methacrylate and 2-ethoxyethyl methacrylate, and It is preferable to have a high Tg constituent unit derived from at least one monomer selected from the group consisting of methyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate in combination.

The polymer dispersant of the present disclosure includes at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and a hydrocarbon group and a hydrocarbon group substitution. At least one selected from the thermally latent building blocks derived from an ethylenically unsaturated monomer containing a carboxy group protected by a structure derived from a vinyl ether compound containing a silyl group or a hydrocarbon group in the side chain is adjacent to each other. Examples thereof include copolymers having a structure in which ethylene is located, and may further have other structural units. Examples of the copolymer include a random copolymer, a block copolymer, a graft copolymer and the like.
The polymer dispersant of the present disclosure includes at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and the general formula (II). A block copolymer having a structural unit represented by, or at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'). A graft copolymer having a structural unit represented by the general formula (III) described later is preferable from the viewpoint of improving dispersibility and dispersion stability.

<Block copolymer>
The block copolymer preferable as the polymer dispersant of the present disclosure includes at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and the general. It is a block copolymer having a structural unit represented by the formula (II).
The block copolymer has a block portion having at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and the general formula (II). It is preferable that it is a block copolymer having a block portion having a structural unit represented by.

(A block portion containing at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'))
The block copolymer preferably has a block portion containing at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'). Since the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') are as described above, the description thereof is omitted here.
In the block portion containing at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), the structural unit represented by the general formula (I) and the general formula ( It is preferable that three or more structural units represented by I') are included. Among them, from the viewpoint of improving dispersibility and improving heat resistance, it is preferable to include 3 or more and 200 or less, more preferably 3 or more and 50 or less, and further include 3 or more and 30 or less. Is even more preferable.
At least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') only needs to function as a color material affinity site, and is composed of one type. It may contain two or more kinds of structural units.

In the block copolymer, the total content ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') is 100% by mass of the entire block copolymer. It is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 55% by mass or less, and further preferably 25% by mass or more and 52% by mass or less.

(Block portion having a structural unit represented by the general formula (II))
By having the structural unit represented by the general formula (II) in the block portion, the block copolymer suppresses fading of the colored layer, improves the brightness, and further thins the colored layer. In addition, the solvent affinity is improved, and the dispersibility and dispersion stability of the colorant are improved. Since the structural unit represented by the general formula (II) is as described above, the description thereof is omitted here.

Further, the block portion having the structural unit represented by the general formula (II) further has the low Tg structural unit, so that the solvent solubility of the colored resin composition and the adhesion of the colored layer to the substrate are compatible. It is preferable to have the low Tg structural unit and the high Tg structural unit from the viewpoint of solvent solubility of the colored resin composition, substrate adhesion of the colored layer, and solvent resistance.
Since the low Tg constituent unit and the high Tg constituent unit are as described above, the description thereof is omitted here.

The block portion having the structural unit represented by the general formula (II) may further include other structural units different from the above-mentioned structural unit. Examples of the other structural unit include a structural unit containing a hydrocarbon group substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxy group, an amino group, an epoxy group, an isocyanate group, and a hydrogen bond forming group in the side chain. , A structural unit to which a polymerizable group is added by reacting a compound having a functional group and a polymerizable group that reacts with the substituent after synthesizing a block copolymer having these substituents can be mentioned.

The content ratio of the structural unit represented by the general formula (II) in the block portion having the structural unit represented by the general formula (II) is 100 mass when the entire block portion is 100% by mass. It may be%. On the other hand, from the viewpoint of dispersibility, it is preferably 10% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and further preferably 30% by mass or more and 50% by mass or less. preferable.
Further, the content ratio of the low Tg structural unit in the block portion having the structural unit represented by the general formula (II) is 10% by mass or more and 70% by mass when the entire block portion is 100% by mass. It is preferably 15% by mass or more, and more preferably 50% by mass or less.
Further, the content ratio of the high Tg structural unit in the block portion having the structural unit represented by the general formula (II) is 10% by mass or more and 60% by mass when the entire block portion is 100% by mass. It is preferably 15% by mass or more, and more preferably 50% by mass or less.

The number of the constituent units constituting the block portion having the constituent units represented by the general formula (II) is not particularly limited, but the solvent-affinity portion and the color material-affinity portion are effectively formed while improving the heat resistance. From the viewpoint of acting and improving the dispersibility of the coloring material, it is preferably 10 or more and 200 or less, more preferably 10 or more and 100 or less, and further preferably 10 or more and 70 or less.

In the block copolymer, the content ratio of the structural unit represented by the general formula (II) is 20% by mass or more and 95% by mass or less when the whole block copolymer is 100% by mass. It is preferably 30% by mass or more and 90% by mass or less.

The block portion having the structural unit represented by the general formula (II) may be selected so as to function as a solvent-affinity site, and two or more types of structural units are randomly arranged in the block portion. It may be arranged in blocks.

In the block copolymer, the number of units m of the structural unit of the block portion having at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and The ratio m / n of the number n of the structural units of the block portion having the structural unit represented by the general formula (II) is preferably in the range of 0.01 or more and 1 or less, and is 0.05 or more. It is more preferably in the range of 0.7 or less from the viewpoints of dispersibility and dispersion stability of the coloring material, heat resistance, brightness of the colored layer and thinning.

As the bonding order of the block copolymer, a block portion having at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') and the general formula ( It suffices as long as it has a block portion having a structural unit represented by II) and can stably disperse the coloring material, and is not particularly limited, but the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I) and A block portion having at least one selected from the structural units represented by the general formula (I') is bonded to only one end of the block copolymer, which is excellent in interaction with the coloring material and is a dispersant. It is preferable because it can effectively suppress the aggregation of each other.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 2500 or more and 200,000 or less, and is preferably 3000 or more and 180,000 or less, from the viewpoint of good dispersibility and excellent heat resistance. More preferably, it is more preferably 5000 or more and 170000 or less.

In the present disclosure, the number average molecular weight Mn and the weight average molecular weight Mw are values measured by GPC (gel permeation chromatography). Measurement, using HLC-8220GPC of Tosoh, elution solvent and the 0.01 mol / L of lithium bromide was added N- methylpyrrolidone (NMP), a polystyrene standard calibration curve Mw: 8 × ¹⁰ 5 (F -80), Mw: 4 × 10 ⁵ (F-40), Mw: 2 × 10 ⁵ (F-20), Mw: 1 × 10 ⁵ (F-10), Mw: 4 × 10 ⁴ (F-4) ), Mw: 2 × 10 ⁴ (F-2), Mw: 5 × 10 ³ (A-5000), Mw: 2.5 × 10 ³ (A-2500), Mw: 1 × 10 ³ (A-1000) ), Mw: 5 × 10 ² (A-500) (all manufactured by Tosoh), and the measurement column was TSK-GEL ALPHA-M × 2 (manufactured by Tosoh).

<Graft copolymer>
The preferred graft copolymer as the polymer dispersant of the present disclosure includes at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and the following general. It is a graft copolymer having a structural unit represented by the formula (III).

（一般式（ＩＩＩ）中、Ｒ^８は水素原子又はメチル基、Ｌ^２は直接結合又は２価の連結基を表し、Ｐｏｌｙｍｅｒは、下記一般式（ＩＶ）で表される構成単位を有するポリマー鎖を表す。）

(In the general formula (III), R ⁸ represents a hydrogen atom or a methyl group, L ² represents a direct bond or a divalent linking group, and Polymer is a polymer chain having a structural unit represented by the following general formula (IV). Represents.)

（一般式（ＩＶ）中、Ｒ^９は水素原子又はメチル基を表し、Ｒ^Ｐ’は下記一般式（Ａ’）で表される１価の保護基を表す。ｎは５以上２００以下の整数を表す。）

(In the general formula (IV), R ⁹ is a hydrogen atom or a methyl group, R P ^'is the following general formula (A' .n representing a monovalent protecting group represented by) 5 to 200 integer Represents.)

（一般式（Ａ’）中、Ｒ^Ｐ’１は、炭素原子又はケイ素原子を表し、Ｒ^Ｐ’２、Ｒ^Ｐ’３及びＲ^Ｐ’４はそれぞれ独立に、水素原子又は炭化水素基を表し、Ｒ^Ｐ’５は、炭化水素基又は−ＯＲ^Ｐ’６を表し、Ｒ^Ｐ’６は炭化水素基を表す。Ｒ^Ｐ’４及びＲ^Ｐ’５は互いに結合して環構造を形成してもよい。）

(In the general formula (A '), ^{R P'1} represents a carbon atom or a silicon atom, ^{R P'2, R P'3} and ^{R P'4} each independently represent a hydrogen atom or a hydrocarbon group , ^{R P'5} represents a hydrocarbon group or -OR ^{P'6, R P'6} is .R ^P'4 and ^{R P'5} represents a hydrocarbon group bonded to form a ring system with one another May be good.)

Since the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') are as described above, the description thereof is omitted here.

In the general formula (III), the ^{divalent linking group in L 2} is the same as in ^{L 1 of the} general formula (I). The ^{direct bond of L 2} means that the Polymer is directly bonded to the carbon atom without interposing a linking group. Above all, from the viewpoint of dispersibility, L ² in the general formula (III) is preferably a divalent linking group containing a −COO− group.
The Polymer in the general formula (III) is a polymer chain having a structural unit represented by the general formula (IV). In Formula (IV), R P ^'is the general formula (A' represents a monovalent protecting group represented by). ^{R P'1} in the general formula ^{(A '), R P'2,} R P'3, R P'4 and ^{R P'5 is, R} P1, ^R P2 in each of the general formulas ^{(A), R P3} , R ^P4 and R ^P5 .

The polymer chain may be a homopolymer or a copolymer of the structural unit represented by the general formula (IV). Further, the polymer chain contained in the structural unit represented by the general formula (III) may be used alone or in combination of two or more in the graft copolymer.

The polymer in the general formula (III) is a polymer chain having the low Tg structural unit in addition to the structural unit represented by the general formula (IV). It is preferable from the viewpoint that the solvent resolubility of the colored resin composition can be improved, and further, the polymer chain having the low Tg constitutional unit and the high Tg constitutional unit is preferable, and the solvent solubility and the colored resin composition are It is more preferable from the viewpoint of solvent resolubility of solid content and solvent resistance.
Since the low Tg constituent unit and the high Tg constituent unit are as described above, the description thereof is omitted here.

The polymer chain may further contain other structural units that are different from the structural units described above. Examples of the other structural units include those similar to the other structural units that may be included in the block portion having the structural unit represented by the general formula (II) of the block copolymer described above. ..

The content ratio of the structural unit represented by the general formula (IV) in the polymer chain represented by Polymer in the general formula (III) improves the brightness of the colored layer after the heating step, and the film thickness of the colored layer. From the viewpoint of reducing the amount of the polymer chain, the larger the amount, the more preferable. The content ratio of the structural unit represented by the general formula (IV) is preferably 10% by mass or more, preferably 10% by mass or more, from the viewpoint of improving the brightness of the colored layer after the heating step and reducing the film thickness of the colored layer. It is more preferably mass% or more, and further preferably 30 mass% or more. On the other hand, in consideration of the balance between dispersibility, solvent solubility, substrate adhesion of the colored layer, and other physical properties such as solvent resistance, other configurations such as the low Tg constituent unit and the high Tg constituent unit are considered. From the viewpoint of containing units, when the entire polymer chain is taken as 100% by mass, it is preferably 80% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less. More preferred.
Further, the content ratio of the low Tg constituent unit in the polymer chain is preferably 10% by mass or more and 60% by mass or less, preferably 15% by mass or more and 50% by mass, when the entire polymer chain is 100% by mass. More preferably, it is less than%.
Further, the content ratio of the high Tg constituent unit in the polymer chain is preferably 10% by mass or more and 60% by mass or less, preferably 15% by mass or more and 50% by mass, when the entire polymer chain is 100% by mass. More preferably, it is less than%.

The polymer chain having the structural unit represented by the general formula (IV) may be selected so as to function as a solvent-affinity site, and two or more structural units are randomly arranged in the polymer chain. It may be arranged in a block.

In the general formula (III), the weight average molecular weight Mw of the polymer chain in Polymer is preferably in the range of 500 or more and 15,000 or less, and more preferably in the range of 1000 or more and 8000 or less.
As a guide, the polymer chain in Polymer preferably has a solubility of 50 (g / 100 g solvent) or more at 23 ° C. with respect to the organic solvent used in combination.
The solubility of the polymer chain can be determined by the fact that the raw material into which the polymer chain is introduced when preparing the graft copolymer has the solubility. For example, when a polymerizable oligomer containing a polymer chain and a group having an ethylenically unsaturated double bond at the end thereof is used to introduce the polymer chain into the graft copolymer, the polymerizable oligomer has the solubility. Just do it. Further, after the copolymer is formed by the monomer containing a group having an ethylenically unsaturated double bond, a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer is used. When introducing a polymer chain, it is sufficient that the polymer chain containing the reactive group has the solubility.

Further, in the graft copolymer, the total content of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') is 5% by mass or more and 60% by mass or less. It is more preferable, it is more preferably 10% by mass or more and 55% by mass or less, and even more preferably 25% by mass or more and 52% by mass or less. If the total content of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') in the graft copolymer is within the above range, the coloring material in the graft copolymer Since the ratio of the affinity site with the above is appropriate and the decrease in solubility in the organic solvent can be suppressed, the adsorptivity to the coloring material is improved, and excellent dispersibility and dispersion stability can be obtained.
On the other hand, in the graft copolymer, the structural unit represented by the general formula (III) is preferably contained in a proportion of 40% by mass or more and 95% by mass or less, and 45% by mass or more and 90% by mass or less. Is more preferable, and 48% by mass or more and 75% by mass or less is further preferable.

The weight average molecular weight Mw of the graft copolymer is not particularly limited, but is preferably in the range of 1000 or more and 200,000 or less from the viewpoint of good dispersibility and excellent heat resistance, and is preferably 3000 or more and 150,000 or less. It is more preferable that it is within the range of 5,000 or more and 100,000 or less.

The graft copolymer used in the present disclosure includes at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'), and the general formula (III). In addition to the structural unit represented by), other structural units may be provided. An ethylenically unsaturated double bond-containing monomer copolymerizable with the ethylenically unsaturated double bond-containing monomer or the like that induces the structural unit represented by the general formula (I) is appropriately selected and copolymerized, and the like. Constituent units can be introduced.

<Manufacturing of polymer dispersant>
The method for producing a polymer dispersant according to the present disclosure comprises a copolymer containing at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'). Any method can be produced, and the method is not particularly limited. At least one structural unit selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I') is, for example, a monomer represented by the following general formula (Ia). , A method of copolymerizing with another monomer by a known polymerization method to obtain a copolymer.

（一般式（Ｉａ）中、Ｒ^１、Ｒ^２、及びＬ^１は、一般式（Ｉ）と同様である。）

(In the general formula (Ia), R ¹ , R ² , and L ¹ are the same as those in the general formula (I).)

Alternatively, for example, an organic phosphonic acid is added to the reactive group of a copolymer having a structural unit having one or more reactive groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group. May have a step of reacting.

The method for producing a block copolymer preferable as the polymer dispersant according to the present disclosure is at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'). It is not particularly limited as long as it is a method capable of producing a block copolymer having a block portion containing the above and a block portion containing the structural unit represented by the general formula (II). When producing a block copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), for example, a monomer represented by the general formula (Ia). And a method of copolymerizing a monomer for inducing a structural unit represented by the general formula (II) with a known polymerization method such as living polymerization to obtain a block copolymer.

Alternatively, for example, a monomer having a reactive group such as a glycidyl group, an alicyclic epoxy group, an oxetane group, or a hydroxyl group and an ethylenically unsaturated double bond, and a structural unit represented by the general formula (II) are derived. after a monomer for synthesizing the copolymer to block copolymer by a known polymerization method living polymerization, organophosphonate having a desired structure ^{(R 2 P (= O)} (OH) 2), wherein Examples thereof include a method of forming a structural unit represented by the general formula (I) by adding it to a structural unit derived from a monomer having a reactive group.

Further, when a block copolymer having a structural unit represented by the general formula (I') and a structural unit represented by the general formula (II) is produced, it is represented by the general formula (I). After producing a block copolymer having a structural unit and a structural unit represented by the general formula (II), a salt-forming agent containing an organic cation is further added, and the mixture is heated and stirred as necessary. A method of forming a salt between the acidic phosphorus compound group and the organic cation of the structural unit represented by the general formula (I) to obtain the structural unit represented by the general formula (I'). Can be mentioned. The salt-forming agent may be appropriately selected according to the organic cation to be introduced. For example, when a protonated nitrogen-containing organic cation is introduced as an organic cation, various corresponding tertiary amine compounds and imidazole compounds can be used. The amount of the salt forming agent added may be appropriately adjusted according to the ratio of the constituent units to be introduced, as long as good dispersibility and dispersion stability are exhibited, but is generally represented by the above general formula (I). It is about 0.05 to 1.00 molar equivalents, preferably 0.3 to 0.5 molar equivalents, relative to the phosphorus moiety contained in the constituent unit.

The method for producing a graft copolymer preferable as the polymer dispersant according to the present disclosure is at least one selected from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (I'). Any method can be used as long as it can produce a graft copolymer having the above-mentioned structural unit represented by the general formula (III), and is not particularly limited. When producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (III), for example, a monomer represented by the general formula (Ia). And a polymer chain having at least one structural unit represented by the general formula (IV) and an ethylenically unsaturated double bond at the end thereof, which induces the structural unit represented by the general formula (III). Examples thereof include a method in which a polymerizable oligomer composed of a group is contained as a copolymerization component and copolymerized to produce a graft copolymer.
Alternatively, as a method for producing a graft copolymer, a polymer chain having at least one structural unit represented by the general formula (IV) and a terminal thereof, which induces the structural unit represented by the general formula (III). After copolymerizing a polymerizable oligomer composed of a group having an ethylenically unsaturated double bond with a monomer having a reactive group such as a glycidyl group, an organic phosphonic acid having a desired structure (R ² P (= O)) ) (OH) ² ) is added to a structural unit derived from a monomer having a reactive group to obtain a structural unit represented by the general formula (I). Further, when a graft copolymer having a structural unit represented by the general formula (I') and a structural unit represented by the general formula (III) is produced, it is represented by the general formula (I). After producing a graft copolymer having a structural unit and a structural unit represented by the general formula (III), a salt-forming agent containing an organic cation is further added as in the production of the block copolymer. , A method of using the structural unit represented by the general formula (I') can be mentioned.

The method for producing the polymer dispersant of the present disclosure includes, among others, a common weight having a structural unit having one or more reactive groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group. From the viewpoint of reactivity, a method for producing a polymer dispersant, which comprises a step of reacting an organic phosphonic acid with the reactive group of the coalescence, is preferable, and further, the structural unit represented by the general formula (II) is used. Organic phosphonic acid is added to the reactive group of the block copolymer having a structural unit having one or more reactive groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group. Reaction process or
A graft having a structural unit represented by the general formula (III) and a structural unit having one or more reactive groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group. A method for producing a polymer dispersant, which comprises any one of a steps of reacting an organic phosphonic acid with the reactive group of the polymer, is preferable from the viewpoint of reactivity.
When such a production method is used, the polymer dispersant of the present disclosure has a structure of a phosphoric acid diester in which a phosphoric acid group (P-OH group) of the general formula (I) has reacted, a glycidyl group, and a fat. It may have a structure in which a ring epoxy group or an oxetane group reacts with each other, or a structure in which an epoxy ring or an oxetane ring is opened. When the polymer dispersant of the present disclosure contains the structure of the phosphoric acid diester or the structure in which the glycidyl group, the alicyclic epoxy group, or the oxetane group react with each other, a cross-linking reaction occurs between the copolymers. It is estimated to be.
The structure can be obtained by appropriately adjusting the reaction conditions for reacting the reactive group with an organic phosphonic acid.
Further, as a method for analyzing the structure of the polymer dispersant of the present disclosure, NMR, IR, GC-MS, XPS, TOF-SIMS, GPC and a combination method thereof can be applied.

2. Color Material Dispersion Liquid The color material dispersion liquid according to the present disclosure contains (A) a color material, (B) a dispersant, and (C) a solvent, and the (B) dispersant according to the present disclosure. Contains a polymer dispersant.

In the color material dispersion liquid according to the present disclosure, the dispersant (B) contains the polymer dispersant according to the present disclosure, so that the change in chromaticity after high temperature heating is suppressed, the brightness is improved, and more. A thinned coating film or colored layer can be formed.
Since the polymer dispersant according to the present disclosure contained in the dispersant (B) contained in the color material dispersion liquid according to the present disclosure has been described above, the description thereof will be omitted here. As long as the effect of the color material dispersion liquid according to the present disclosure is not impaired, the dispersant (B) may further contain other conventionally known dispersants.
Hereinafter, the (A) color material, the (C) solvent, and other components that may be contained in the color material dispersion liquid according to the present disclosure will be described.

[(A) Color material]
The color material (A) used in the color material dispersion liquid according to the present disclosure can be appropriately selected and used from those capable of obtaining a desired color tone, and known organic pigments, inorganic pigments, rake color materials and the like can be mentioned. Be done.

Examples of organic pigments include insoluble azo pigments, soluble azo pigments, phthalocyanine organic pigments, quinacridone organic pigments, perylene organic pigments, dioxazine organic pigments, nickel azo pigments, isoindolinone organic pigments, and pyranthron organic pigments. , Thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments, isoindolin organic pigments, quinacridone solid solution pigments, perylene solid solution pigments and other organic solid solution pigments, and other pigments Examples include carbon black.
To exemplify organic pigments by color index (CI) number, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 15, 16, 17, 20, 24, 49, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 120, 123, 124, 125, 126, 127, 128, 129, 130, 133, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 166, 167, 168, 169, 170, 172, 173, 175, 176, 179, 180, 181, 182, 183, 185, 191, 193, 194, 199, 213, 214, 215, 219; C.I. I. Pigment Red 5, 7, 9, 12, 48, 49, 52, 53, 57, 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 83, 88, 89, 97, 112, 122, 123, 144, 146, 147, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 180, 181, 184, 185, 187, 190, 192, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 238, 240, 242, 245, 247, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 268, 269, 270, 272, 279; C.I. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 24, 31, 34, 36, 38, 43, 46, 48, 51, 55, 59, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81; C.I. I. Pigment Violet 1, 2, 3, 3: 1, 3: 3, 5, 13, 19, 23, 25, 27, 29, 30, 31, 32, 36, 37, 38, 40, 42, 50; C.I. I. Pigment Blue 1, 15, 15: 1, 15: 3, 15: 4, 15: 6, 16, 17: 1, 22, 24, 24: 1, 25, 26, 56, 60, 61, 62, 63, 64, 75, 79, 80; C.I. I. Pigment Green 1, 4, 7, 8, 10, 36, 58, 59; C.I. I. Pigment Brown 5, 23, 25, 26, 41 and the like.

Specific examples of the above-mentioned inorganic pigments include barium sulfate, iron oxide, zinc oxide, barium carbonate, barium sulfate, silica, clay, talc, titanium oxide, calcium carbonate, synthetic mica, alumina, zinc oxide, lead sulfate, and yellow lead. Examples thereof include zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and inorganic solid solution pigments.

The colored material dispersion liquid of the present disclosure can preferably use a rake color material having high brightness but relatively poor heat resistance as the color material (A) from the viewpoint of improving the heat resistance of the colored layer, and is colored. From the viewpoint of increasing the brightness of the layer, it is preferable to use a rake color material, and it is more preferable to use a metal rake color material as a dye.
In the present disclosure, the rake coloring material refers to a coloring material in which a dye soluble in a solvent is salt-formed with counter ions to be insolubilized. The rake coloring material can usually be obtained by mixing a dye described later and a rake agent described later in a solvent. The metal lake color material of a dye means a lake color material obtained by using a rake agent containing a metal.
The dye may be appropriately selected according to a desired color tone, and has any basic skeleton (color development site) such as azo dye, anthraquinone dye, triarylmethane dye, xanthene dye, cyanine dye, and indigo dye. ) May be a dye. Further, the dye may be a dye classified into any of the following types, such as an acid dye having an anionic substituent and a basic dye having a cationic substituent.
Further, in the present disclosure, the color material (A) is one or more selected from the group consisting of a triarylmethane color material and a xanthene color material from the viewpoint of color development, light transmission, heat resistance and the like. It is preferable to use a coloring material.

Specific examples of acidic dyes include C.I. I. Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72, C.I. I. Acid Blue 13, 5, 7, 9, 22, 83, 90, 93, 100, 103, 104, 109, C.I. I. Acid greens 3,5,6,7,8,9,11,13,14,15,16,18,22,50,50: 1 etc. Triarylmethane acid dyes; C.I. I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, Sulforhodamine 101, C.I. I. Examples thereof include xanthene-based acid dyes such as Acid Blue 19. Xanthene-based acid dyes include, among others, C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, C.I. I. Acid Violet 9, C.I. I. Acid Violet 30, C.I. I. It is preferably a rhodamine-based acid dye such as Acid Blue 19.

The basic dye is an ionic dye in which the cation part forms a color group. For example, an azine dye, an oxazine dye, a thiazine dye, an azo dye, an anthraquinone dye, a xanthene dye, and a triarylmethane dye. Examples thereof include dyes, phthalocyanine dyes, auramine dyes, acrydin dyes, and methine dyes. Specifically, those having the following color index (CI) names can be mentioned.

C. I. Basic Red 2, 5, 6, 10, C.I. I. Basic Violet 5, 6,
8, 12, C.I. I. Adin dyes such as Basic Yellow 14;
C. I. Oxazine dyes such as Basic Blue 3, 6, 10, 12, 74, 122;
C. I. Basic Blue 9, 17, 24, C.I. I. Thiazine dyes such as Basic Green 5;
C. I. Basic Red 18, 22, 23, 24, 29, 30, 31, 32, 34, 38, 39, 46, 51, 53, 54, 55, 62, 64, 76, 94, 111, 118, C.I. I. Basic Blue 41, 53, 54, 55, 64, 65, 66, 67, 162, C.I. I. Basic Violet 15, 16, 18, 21, 22, 36, C.I. I. Basic Yellow 15, 19, 24, 25, 28, 29, 38, 39, 49, 51, 52, 53, 57, 62, 73, C.I. I. Azo dyes such as Basic Orange 1, 2, 24, 25, 29, 30, 33, 54, 69;
C. I. Anthraquinone dyes such as Basic Blue 22, 44, 47, 72;
C. I. Basic Red 1, 1: 1, 3, 4, 8, 11, C.I. I. Xanthene dyes such as Basic Violet 10, 11, 11: 1;
C. I. Basic Red 9, C.I. I. Basic Blue 1, 2, 5, 7, 8, 11, 15, 18, 20, 23, 26, 35, 81, C.I. I. Basic Violet 1, 2, 3, 4, 14, 23, C.I. I. Triarylmethane dyes such as Basic Green 1 and 4;
C. I. Phthalocyanine dyes such as Basic Blue 140;
C. I. Auramine dyes such as Basic Yellow 2, 3, 37;
C. I. Basic Yellow 5, 6, 7, 9, C.I. I. Acridine dyes such as Basic Orange 4, 5, 14, 15, 16, 17, 18, 19;
C. I. Basic Red 12, 13, 14, 15, 27, 28, 37, 52, 90, C.I. I. Basic Blue 62, 63, C.I. I. Basic Yellow 11, 13, 21, 22, 28, 29, 49, 51, 52, 53, C.I. I. Methine dyes such as basic violet 7, 15, 16, 20, 21, 22.
Further, as the triarylmethane-based basic dye and the xanthene-based basic dye in the present disclosure, cationic dyes constituting the coloring material represented by the general formula (VII) described later are also preferable.
These dyes can be used alone or in combination of two or more.

In the rake coloring material, the counter ion differs depending on the type of the dye, the counter ion of the acid dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the counter ion is appropriately selected and used according to the above dye. That is, when the acid dye is insolubilized, a compound that produces a counter cation of the dye is used as a rake agent, and when the basic dye is insolubilized, a counter anion of the dye is generated as a rake agent. Compounds are used.

As counter cations of acidic dyes, in addition to ammonium cations, metal cations such as calcium ion, barium ion, strontium ion, manganese ion, aluminum ion, cesium ion, lanthanum ion, neodymium ion, and cerium ion, polyaluminum chloride and oxychloride. Examples include inorganic polymers such as zirconium.
Examples of compounds that generate ammonium ions include primary amine compounds, secondary amine compounds, tertiary amine compounds, and the like. Among them, secondary amine compounds are excellent in heat resistance and light resistance. Alternatively, it is preferable to use a tertiary amine compound.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent. Examples of the anionic group include -SO ₂ N ^- SO ₂ CH ₃ , -SO ₂ N ^- COCH ₃ , -SO ₂ N ^- SO ₂ CF ₃ , -SO ₂ N ^- COCF ₃ , and -CF ₂ SO _{2. ^{N - SO 2 CH 3, -CF}} 2 SO 2 N - COCH 3, -CF 2 SO 2 N - SO 2 CF 3, -CF 2 SO 2 N - COCF 3 or imidate group such as, -SO ₃ ^{-, _{-CF 2 SO 3 -, -PO 3}} 2-, -COO -, -CF 2 PO 3 2-, -CF 2 COO - , and the like. Among these, from the viewpoint of heat resistance and light resistance, and imidate ^{_{groups, -SO 3 -, -CF 2 SO}} 3 - , more preferably a, -SO ₃ ^- (sulfonato group) is more preferable.
On the other hand, the inorganic anion, for example, anions of oxo acids (phosphoric acid ion, chromate ion, tungstate ion _(WO ^{4 2-),} molybdate ions _(MoO ^{4 2-),} etc.) and a plurality of Examples thereof include inorganic anions such as polyacid anion condensed with oxo acid and a mixture thereof.
Examples of the polyoxometalate anion, isopoly acid anion _{(M m} O ^{n) c-} and a even heteropoly acid anion _{(X l} M _m O ⁿ⁾ may be a ^c-. In the above ionic formula, M represents a poly atom, X represents a hetero atom, l represents the composition ratio of the hetero atom, m represents the composition ratio of the poly atom, and n represents the composition ratio of the oxygen atom. Examples of the poly atom M include Mo, W, V, Ti, Nb and the like. Examples of the heteroatom X include Si, P, As, S, Fe, and Co.
Among them, from the viewpoint of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.

Examples of the polyacid anion containing at least one of molybdenum and tungsten include isopolyacids such as tungstate ion [W ₁₀ O ₃₂ ] ^4- , molybdate ion [Mo ₆ O ₁₉ ] ^2- , and heteropolyacid. There are phosphotungstate ion [PW ₁₂ O ₄₀ ] ^3- , silicate tungrate ion [SiW ₁₂ O ₄₀ ] ^4- , phosphomolybdate _{ion [PMo 12} O ₄₀ ] ^3- , lintanguto molybdate ion [PW _{12- x} Mo _x O ₄₀ ] ^3- , Kateangst molybdate ion [SiW _12-x Mo _x O ₄₀ ] ^{4-, and the} like. The polyacid anion containing at least one of molybdenum and tungsten is preferably a heteropolyacid among the above from the viewpoint of heat resistance and easy availability of raw materials, and further, a heteropolyacid containing phosphorus (P). Is more preferable.

Examples of the rake agent that generates an inorganic anion include an alkali salt and an alkali metal salt of the above-mentioned inorganic anion.
The counter anion of the basic dye in the rake coloring material can be used alone or in combination of two or more.

In the present disclosure, the rake color material is preferably a metal rake color material of a basic dye from the viewpoint of heat resistance and light resistance, and at least one metal of a triarylmethane-based basic dye and a xanthene-based basic dye. It is more preferable that the color material is a rake color material, and further, it is excellent in heat resistance and light resistance, and it is preferable to include a color material represented by the following general formula (VII) from the viewpoint of achieving high brightness of the color filter.

（一般式（ＶＩＩ）中、Ａは、Ｎと直接結合する炭素原子がπ結合を有しないａ価の有機基であって、当該有機基は、少なくともＮと直接結合する末端に飽和脂肪族炭化水素基を有する脂肪族炭化水素基、又は当該脂肪族炭化水素基を有する芳香族基を表し、炭素鎖中にＯ、Ｓ、Ｎが含まれていてもよい。Ｂ^ｃ−はｃ価のポリ酸アニオンを表す。Ｒ^ｉ〜Ｒ^ｖは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ^ｉｉとＲ^ｉｉｉ、Ｒ^ｉｖとＲ^ｖが結合して環構造を形成してもよい。Ｒ^ｖｉ及びＲ^ｖｉｉは各々独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基又はハロゲン原子を表す。Ａｒ^１は置換基を有していてもよい２価の芳香族基を表す。
ａ及びｃは２以上の整数、ｂ及びｄは１以上の整数を表す。ｅは０又は１であり、ｅが０のとき結合は存在しない。ｆ及びｇは０以上４以下の整数を表し、ｆ＋ｅ及びｇ＋ｅは０以上４以下である。
複数あるＲ^ｉ〜Ｒ^ｖｉｉ、Ａｒ^１、ｅ、ｆ及びｇはそれぞれ同一であっても異なっていてもよい。）

(In the general formula (VII), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group is at least saturated aliphatic hydrocarbon at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain. B ^c− is a c-valent poly. .R ⁱ to R ^v which represents an acid anion each independently represent a hydrogen atom, which may have an optionally substituted alkyl group or a substituted aryl group, R ⁱⁱ and R ^iii, R ^Iv and ^Rv may be combined to form a ring structure. ^Rvi and ^Rvi may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen. Represents an atom. Ar ¹ represents a divalent aromatic group which may have a substituent.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. f and g represent integers of 0 or more and 4 or less, and f + e and g + e are 0 or more and 4 or less.
The plurality of R ^{i to} R ^vii , Ar ¹ , e, f and g may be the same or different from each other. )

Since the coloring material represented by the above general formula (VII) contains a divalent or higher anion and a divalent or higher cation, in the aggregate of the coloring material, the anion and the cation are simply one molecule to one molecule. It is presumed that they do not form an ionic bond at the site, but form a molecular assembly in which a plurality of molecules are associated via an ionic bond. Therefore, the apparent molecular weight of the coloring material represented by the general formula (VII) is significantly increased as compared with the molecular weight of the conventional rake coloring material. It is presumed that the formation of such molecular aggregates further enhances the cohesive force in the solid state, reduces the thermal motion, suppresses the dissociation of ion pairs and the decomposition of the cation portion, and improves the heat resistance.

A in the general formula (VII) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is at least a saturated fat at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having a group hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and contains O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. It may be. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as color tone and transmittance of the cationic color-developing site are not affected by the linking group A and other color-developing sites, and are not affected by the monomer. Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N is linear, branched or cyclic unless the carbon atom at the terminal directly bonded to N has a π bond. Any of the above, the carbon atom other than the terminal may have an unsaturated bond, or may have a substituent, and O, S, and N are contained in the carbon chain. May be good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group and the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
Further, in A, the aromatic group having an aliphatic hydrocarbon group is a monocyclic or polycyclic aromatic group having at least an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. It may be mentioned and may have a substituent, and may be a heterocycle containing O, S, N.
Among them, from the viewpoint of skeletal robustness, A preferably contains a cyclic aliphatic hydrocarbon group or aromatic group.
As the cyclic aliphatic hydrocarbon group, the alicyclic hydrocarbon group Aribashi is particularly preferable from the viewpoint of skeletal robustness. The alicyclic hydrocarbon group with a bridge refers to a polycyclic aliphatic hydrocarbon group having a bridging structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the alicyclic hydrocarbon groups with bridges, norbornane is preferable. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring, and among them, a group containing a benzene ring is preferable. For example, when A is a divalent organic group, an aromatic group in which two linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms or alkylene groups having 1 to 20 carbon atoms such as xylylene groups are substituted. Examples include tribal groups.

The valence a in the general formula (VII) is the number of color-developing cation sites constituting the cation, and a is an integer of 2 or more. In the coloring material of the present disclosure, since the cation valence a is 2 or more, it is excellent in heat resistance. The upper limit of a is not particularly limited, but from the viewpoint of ease of production, a is preferably 4 or less, and more preferably 3 or less.

The alkyl group in R ^{i to} R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 or more and 20 or less carbon atoms can be mentioned, and among them, a linear or branched alkyl group having 1 or more and 8 or less carbon atoms is preferable, and the number of carbon atoms is 1 or more and 5 or less. The following linear or branched alkyl groups are more preferable from the viewpoint of brightness and heat resistance. Among them, it is particularly preferred alkyl groups in R ⁱ to R ^v is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group and the like, and examples of the substituted alkyl group include a benzyl group and the like.
The aryl group in R ^{i to} R ^v is not particularly limited. For example, a phenyl group, a naphthyl group and the like can be mentioned. Examples of the substituent that the aryl group may have include an alkyl group and a halogen atom.

R ⁱⁱ and R ⁱⁱ , R ^iv and R ^v are combined to form a ring structure means that R ⁱⁱ and R ⁱⁱ , R ^iv and R ^v form a ring structure via a nitrogen atom. To say. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

The ^R i to R ^v Among them from the viewpoints of chemical stability, each independently, a hydrogen atom, the number 1 to 5 of the alkyl group carbon atoms, a phenyl group, ^{or, R ii} and ^{R iii, R iv} and ^{R v} are It is preferable that they are combined to form a pyrrolidine ring, a piperidine ring, and a morpholine ring.

R ^{i to} R ^v can each have the above-mentioned structure independently, but among them, it is preferable that R i is a hydrogen atom from the viewpoint of color purity, and further, from the viewpoint of ease of production and raw material procurement, ^{R i i to R v} . It is more preferable that all ^{Rvs are the same.}

R ^vi and R ^vii each represent an alkyl group which may independently have a substituent, an alkoxy group which may have a substituent, or a halogen atom. The alkyl group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. More preferably. Examples of the alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group, which may be linear or have a branch. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group.
The alkoxy group in R ^vi and R ^vii is not particularly limited, but is preferably a linear or branched alkoxy group having 1 or more and 8 or less carbon atoms, and an alkoxy group having 1 or more and 4 or less carbon atoms. More preferably it is a group. Examples of the alkoxy group having 1 or more and 4 or less carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, which may be linear or have a branch. The substituent that the alkoxy group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group.
Examples of the halogen atom in R ^vi and R ^vii include a chlorine atom and a bromine atom.
Among them, R ^vi and R ^vii are preferably an electron-donating group such as a methyl group or an ethyl group, a methoxy group or an ethoxy group from the viewpoint of heat resistance.
The ^{number of substitutions of R vi} and R ^vii , that is, f and g independently represent integers of 0 or more and 4 or less, and among them, 0 or more and 2 or less are preferable, and 0 or more and 1 or less are more preferable.
Further, R ^vi and R ^vii may be substituted at any site of the triarylmethane skeleton or the aromatic ring having a resonance structure in the xanthene skeleton, and among them, -NR ⁱⁱ R ⁱⁱ or -NR ^iv. it is preferably substituted in the meta position relative to the substitution position of the amino group represented by R ^v.

The ^{divalent aromatic group in Ar 1} is not particularly limited. The aromatic group in Ar ¹ can be the same as that listed in the aromatic group in A.
Ar ¹ is preferably an aromatic group having 6 or more and 20 or less carbon atoms, and more preferably an aromatic group composed of a fused polycyclic carbon ring having 10 or more and 14 or less carbon atoms. Of these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

^{A plurality of R i to} R ^vii , Ar ¹ , e, f and g in one molecule may be the same or different. When a plurality of R ^{i to} R ^vii , Ar ¹ , e, f, and g are the same, the color-developing part shows the same color development, so that the same color as a single color-developing part can be reproduced, and the color purity is high. It is preferable from the point of view. On the other hand, when at least one different substituent among ^{R i ~R vii, Ar 1,} e, f and g, can reproduce the color of a mixture of plural kinds of monomers, the desired Can be adjusted to color.

In the coloring material represented by the general formula (VII), the anion portion (B ^c− ) is a divalent or higher polyacid anion. The polyoxometalate anion, isopolyacid ion _{(M m} O ^{n) c-} and a even heteropoly acid ion _{(X l} M _m O ⁿ⁾ may be a ^c-. In the above ionic formula, M represents a poly atom, X represents a hetero atom, l represents the composition ratio of the hetero atom, m represents the composition ratio of the poly atom, and n represents the composition ratio of the oxygen atom. Examples of the poly atom M include Mo, W, V, Ti, Nb and the like. Examples of the heteroatom X include Si, P, As, S, Fe, and Co. Further, a counter cation such as ^{Na +} or H ^{+ may be partially contained.}
Among them, a polyacid anion containing at least one of tungsten (W) and molybdenum (Mo) is preferable, and at least tungsten is contained and molybdenum is contained, from the viewpoint of high brightness and excellent heat resistance and light resistance. It is more preferable that it is a good polyacid anion from the viewpoint of heat resistance.

Examples of the polyacid anion containing at least one of tungsten (W) and molybdenum (Mo) include isopolyacids, tungstate ion [W ₁₀ O ₃₂ ] ^4- and molybdenum ion [Mo ₆ O ₁₉ ] ^{2. -} or a heteropoly acid, ion phosphotungstic acid ^{_{[PW 12 O 40] 3-,}} [P 2 W 18 O 62] 6-, silicotungstic acid ion _{[SiW 12 O} ^{40] 4-,} phosphomolybdic acid ion [ PMo ₁₂ O ₄₀ ] ^3- , Heteropolymetalate ion [SiMo ₁₂ O ₄₀ ] ^4- , Lintangst molybdenate ion [PW _12-x Mo _x O ₄₀ ] ^3- (x is an integer from 1 to 11), [ P ₂ W _18-y Mo _y O ₆₂ ] ^6- (y is an integer of 1 or more and 17 or less), Ketungst molybdenate ion [SiW _12-x Mo _x O ₄₀ ] ^4- (x is an integer of 1 or more and 11 or less) ) Etc. can be mentioned. The polyacid anion containing at least one of tungsten (W) and molybdenum (Mo) is preferably a heteropolyacid among the above, from the viewpoint of heat resistance and easy availability of raw materials, and further P ( More preferably, it is a heteropolyacid containing phosphorus).

As the polyacid anion in the coloring material represented by the general formula (VII), the above-mentioned anions can be used alone or in combination of two or more, and when two or more are used in combination, the polyacid anion can be used. It is preferable that the ratio of tungsten to molybdenum as a whole is 90: 10 to 100: 0 from the viewpoint of heat resistance and light resistance.

In the general formula (VII), b represents the number of cations, d represents the number of anions in the molecular assembly, and b and d represent integers of 1 or more. When b is 2 or more, a plurality of cations in the molecular assembly may be used alone or in combination of two or more. When d is 2 or more, a plurality of anions in the molecular assembly may be used alone or in combination of two or more, and organic anions and inorganic anions may be used in combination. .. In particular, a desired color can be prepared by combining two or more kinds of dyes.

E in the general formula (VII) is an integer of 0 or 1. e = 0 represents the triarylmethane skeleton and e = 1 represents the xanthene skeleton. A plurality of e may be the same or different. That is, for example, it may be a cation moiety having only a triarylmethane skeleton or a plurality of xanthene skeletons, or a cation moiety containing both a triarylmethane skeleton and a xanthene skeleton in one molecule. From the viewpoint of color purity, it is preferable that the cation portion has only the same skeleton. On the other hand, the color material represented by the general formula (VII) can be adjusted to a desired color by forming a cation portion containing both a triarylmethane skeleton and a xanthene skeleton.

Further, as the coloring material used in the present disclosure, a metal lake coloring material of a dye having a thermal decomposition temperature of 230 ° C. or higher is discolored by heating before the structure represented by the general formula (II-a) is developed. This is preferable because the heat resistance and brightness can be easily improved by combining with the polymer dispersant according to the present disclosure. Examples of the metal lake coloring material of the dye having a thermal decomposition temperature of 230 ° C. or higher include the coloring material described in Japanese Patent No. 5403175.
The thermal decomposition temperature of the dye can be measured by thermogravimetric-differential thermal analysis (TG-DTA). Specifically, for example, using a DTG-60A manufactured by Shimadzu Corporation, the heating rate is set to 10 ° C./min, the temperature is raised from 30 ° C. to 600 ° C. in a nitrogen atmosphere, and the thermal decomposition temperature is measured.

(A) The average dispersed particle size of the coloring material is not particularly limited as long as it can develop a desired color, and varies depending on the type of coloring material used, but the dispersion stability of the coloring material is good. From the viewpoint of obtaining sufficient coloring power, it is preferably in the range of 5 nm or more and 300 nm or less, and more preferably in the range of 30 nm or more and 200 nm or less.

The content of the coloring material (A) is not particularly limited as long as a desired colored layer can be formed, and is appropriately adjusted. Specifically, although it varies depending on the type of coloring material, it is preferably in the range of 0.05% by mass or more and 20% by mass or less with respect to the total amount of the coloring material dispersion liquid, and is 1% by mass or more and 15% by mass or less. It is more preferable that it is within the range of.

[(C) Solvent]
The solvent (C) contained in the color material dispersion liquid according to the present disclosure does not react with each component in the color material dispersion liquid, and can be appropriately selected and used from the solvents capable of dissolving or dispersing them. can. Specifically, organic solvents such as alcohol-based; ether alcohol-based; ester-based; ketone-based; ether alcohol acetate-based; ether-based; aprotonic amide-based; lactone-based; unsaturated hydrocarbon-based; saturated hydrocarbon-based Above all, it is preferable to use an ester solvent from the viewpoint of solubility at the time of dispersion and coating suitability.

Preferred ester solvents include, for example, methyl methoxypropionate, ethyl ethoxypropionate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate and methoxybutyl. Acetate, ethoxyethyl acetate, ethyl cellosolve acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,6-hexanediol diacetate, diethylene glycol monoethyl ether acetate, Examples thereof include diethylene glycol monobutyl ether acetate.
Of these, propylene glycol monomethyl ether acetate (PGMEA) is preferably used because it has a low risk to the human body and has low volatility near room temperature but good heat-drying property. In this case, there is an advantage that a special cleaning step is not required even when switching to the colored resin composition using the conventional PGMEA.
These solvents may be used alone or in combination of two or more.

[Other ingredients]
The color material dispersion liquid according to the present disclosure may further contain a dispersion auxiliary resin and other components, if necessary, as long as the effects of the present disclosure are not impaired.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the colored resin composition described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, which may have the effect of stabilizing the dispersion and reducing the amount of the dispersant due to the effect of stabilizing the dispersion.
Other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, a defoaming agent, an anti-repellent agent, an antioxidant, an antioxidant, and an ultraviolet absorber. And so on.

The color material dispersion liquid according to the present disclosure is suitably used as a preliminary preparation for preparing a colored resin composition described later. That is, the color material dispersion liquid is (mass of color material component in composition) / (mass of solid content other than color material component in composition) prepared in advance in the stage before preparing the color resin composition described later. ) A colorant dispersion with a high ratio. Specifically, the ratio (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 color material dispersion liquid and at least the binder component, a colored resin composition having excellent dispersibility can be prepared.
In the present disclosure, the solid content means all components other than the solvent.

[Manufacturing method of color material dispersion liquid]
The method for producing a color material dispersion liquid of the present disclosure contains (A) a color material, (B) a dispersant, (C) a solvent, and various additive components used as desired, and the (A) color material contains. Any method may be used as long as it can be uniformly dispersed in the solvent (C) by the dispersant (B), and can be uniformly dispersed by mixing using a known mixing means.
For example, (B) a dispersant is mixed with (C) a solvent and stirred to prepare a dispersant solution, and then (A) a coloring material and other components are mixed with the dispersant solution, if necessary, and known. A method of dispersing using a stirrer or a disperser of the above can be mentioned.

Examples of the disperser for performing the dispersion treatment include a roll mill such as a two-roll and three-roll mill, a ball mill such as a ball mill and a vibrating ball mill, a paint conditioner, a continuous disc type bead mill, and a bead mill such as a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 mm or more and 2.00 mm or less, and more preferably 0.10 mm or more and 1.0 mm or less.

Specifically, pre-dispersion may be performed with 2 mm zirconia beads having a relatively large bead diameter, and then main dispersion may be performed with 0.1 mm zirconia beads having a relatively small bead diameter. Further, after dispersion, it is preferable to filter with a membrane filter of 0.5 μm or more and 5.0 μm or less.

The viscosity of the color material dispersion liquid according to the present disclosure is not particularly limited, but the shear viscosity at a shear rate of 60 rpm is preferably 10 mPa · s or less from the viewpoint of good dispersibility and good handleability. , 7 mPa · s or less is more preferable. The measurement of the shear viscosity can be performed using a known viscoelasticity measuring device, and is not particularly limited, and can be measured, for example, using a “rheometer MCR301” manufactured by Antonio Par.

3. 3. Colored Resin Composition The colored resin composition according to the present disclosure contains the coloring material dispersion liquid according to the present disclosure, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. do.
Since the colored resin composition according to the present disclosure contains the coloring material dispersion liquid according to the present disclosure, the change in chromaticity after heating at a high temperature is suppressed, the brightness is improved, and a thinner colored layer is formed. be able to.
Since the color material dispersion liquid contained in the colored resin composition according to the present disclosure is the same as the color material dispersion liquid according to the present disclosure described above, the description thereof is omitted here. Hereinafter, (D) alkali-soluble resin, (E) polyfunctional monomer, (F) photoinitiator, and optional additive components that may be contained in the colored resin composition according to the present disclosure will be described.

[(D) Alkali-soluble resin]
The alkali-soluble resin in the present disclosure has an acidic group, acts as a binder resin, and is appropriately selected and used as long as it is soluble in a developing solution used for pattern formation, particularly preferably an alkaline developing solution. be able to.
The preferred alkali-soluble resin in the present disclosure is preferably a resin having a carboxy group as an acidic group, specifically, a (meth) acrylic copolymer having a carboxy group and an epoxy (meth) acrylate having a carboxy group. Examples include resin. Among these, 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 are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, these (meth) acrylic copolymers and the epoxy (meth) acrylate resin may be used by mixing two or more kinds.

The (meth) acrylic copolymer having a carboxy group is obtained by copolymerizing a carboxy group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The (meth) acrylic copolymer having a carboxy group may further contain a structural unit having an aromatic carbocycle. The aromatic carbocycle functions as a component for improving the strength of the film in the colored resin composition.
The acrylic copolymer having a carboxy group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the colored resin composition, but also functions as a component that improves solubility in a solvent and further improves solvent resolubility.

Specific examples of the (meth) acrylic copolymer having a carboxy group include those described in International Publication No. 2012/144521, and specifically, for example, methyl (meth) acrylate. , Ethyl (meth) acrylate and the like which do not have a carboxy group, and one or more selected from (meth) acrylic acid and its anhydride can be exemplified as a copolymer. Further, a polymer in which an ethylenically unsaturated bond is introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above-mentioned copolymer can also be exemplified. It is not limited to.
Among these, a polymer or the like in which an ethylenically unsaturated bond is introduced by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly preferable in that the colored layer becomes more stable.

The copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer in the carboxy group-containing copolymer is 5% by mass or more from the viewpoint that the obtained coating film has good solubility in an alkaline developing solution and pattern formation is facilitated. It is preferably, and more preferably 10% by mass or more. Further, the copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer in the carboxy group-containing copolymer is from the viewpoint of suppressing the formed pattern from falling off from the substrate and the film roughness on the pattern surface during development with an alkaline developer. , 50% by mass or less, and more preferably 40% by mass or less.

The preferable weight average molecular weight of the carboxy group-containing copolymer is preferably 1,000 or more, more preferably 3,000 or more, and is developed with an alkaline developer, from the viewpoint of suppressing deterioration of the binder function after curing. It is preferably 200,000 or less, more preferably 50,000 or less, from the viewpoint of facilitating pattern formation from time to time. The weight average molecular weight is determined by gel permeation chromatography (GPC) as a standard polystyrene conversion value.

The epoxy (meth) acrylate resin having a carboxy group is not particularly limited, but is an epoxy (meth) obtained by reacting a reaction product of an epoxy compound with an unsaturated group-containing monocarboxylic acid with an acid anhydride. Epoxy compounds are suitable.
The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones and used. Specific examples include those described in International Publication No. 2012/144521. The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride may be used alone or in combination of two or more.

The alkali-soluble resin used in the colored resin composition may be used alone or in combination of two or more, and the content thereof is colored from the viewpoint of obtaining sufficient alkali developability. It is preferably 10 parts by mass or more, more preferably 25 parts by mass or more with respect to 100 parts by mass of the coloring material contained in the resin composition, so that the coloring material can be sufficiently contained and a sufficient coloring concentration is obtained. The content of the alkali-soluble resin is preferably 500 parts by mass or less, and more preferably 300 parts by mass or less, based on 100 parts by mass of the coloring material contained in the colored resin composition.

[(E) Polyfunctional Monomer]
The polyfunctional monomer used in the colored resin composition of the present disclosure may be one that can be polymerized by a photoinitiator described later, and a compound having two or more ethylenically unsaturated double bonds is usually used, and in particular, a compound having two or more ethylenically unsaturated double bonds is used. It is preferably a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups.
As the polyfunctional (meth) acrylate, a conventionally known one may be appropriately selected and used. Specific examples include those described in International Publication No. 2012/144521. Further, as the polyfunctional monomer, it is preferable to use a polyfunctional (meth) acrylate having no acidic group from the viewpoint of solvent resistance.

One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination. Further, when the colored resin composition of the present disclosure is required to have excellent photocurability (high sensitivity), the polyfunctional monomer has three or more polymerizable double bonds (trifunctional). Those are preferable, and poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable. Succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate succinic acid Modified products, dipentaerythritol hexa (meth) acrylate and the like are preferable.

<Phosphorus atom-containing polyfunctional monomer>
Further, when the polyfunctional monomer used in the colored resin composition of the present disclosure contains a phosphorus atom-containing polyfunctional monomer, the change in chromaticity after high-temperature heating is further suppressed, the brightness is improved, and the solvent resistance is improved. It is preferable from the viewpoint of improvement. Under high temperature heating, active oxygen increases, while vibration due to heat is transmitted to the color material molecules, and the molecular motion of the color material molecules becomes intense. It is presumed that the color material molecules that are violently moving in this way are easily oxidized by the surrounding active oxygen, and that the color material molecules are decomposed to cause discoloration. On the other hand, the phosphorus atom-containing polyfunctional monomer has an antioxidant function such as stabilizing hydroperoxide generated from active oxygen, and the phosphorus atom is heavier than the carbon atom and has a lower frequency due to heat. , It is presumed that it has a function to make it difficult for vibration due to heat to be transmitted to the coloring material. Further, since the phosphorus atom-containing polyfunctional monomer has a large specific gravity, the phosphorus atom density around the coloring material increases, and further, it becomes difficult for vibration due to heat to be transmitted to the coloring material, so that oxidation is suppressed. Presumed. Normally, active oxygen increases under high-temperature heating, but as described above, the effect of reducing hydroperoxide and the like in the coating film due to the phosphorus atom-containing polyfunctional monomer and the effect of suppressing vibration due to heat of the coloring material. As a result of the synergistic effect with, it is presumed that even under post-baking by heating at a high temperature of 230 ° C. or higher after the coating film is formed, it contributes to the suppression of fading of the coloring material and a colored layer having high brightness can be obtained. Further, it is presumed that the phosphorus atom-containing polyfunctional monomer has a large specific gravity because it contains a phosphorus atom, and as a result of the cross-linking reaction at a higher density in the cured film, the permeation of the solvent is suppressed and the solvent resistance is improved. Will be done.
On the other hand, when the colored resin composition contains a phosphorus atom-containing polyfunctional monomer, the formed colored layer tends to have poor adhesion to the substrate. On the other hand, the colored resin composition according to the present disclosure suppresses a decrease in substrate adhesion even if it contains a phosphorus atom-containing polyfunctional monomer by containing the above-mentioned polymer dispersant according to the present disclosure. be able to. This is because the adhesion between the colored layer and the substrate is improved by containing the phosphoric acid group, and the hydrocarbon group contained in the polymer dispersant according to the present disclosure at the time of post-baking when forming the colored layer. And the protecting group containing at least one of the hydrocarbon group-substituted silyl groups is eliminated to express the carboxy group, so that the affinity between the colored layer and the substrate is improved, and the expressed carboxy group is further transferred to the surface of the substrate. It is presumed that the adhesion between the colored layer and the substrate is further improved by dehydration condensation with the polar groups such as hydroxyl groups.

In the present disclosure, the phosphorus atom-containing polyfunctional monomer may be a compound containing a phosphorus atom and containing two or more polymerizable functional groups in one molecule.
Examples of the polymerizable functional group contained in the phosphorus atom-containing polyfunctional monomer include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and an allyl group. In the present disclosure, the (meth) acrylamide group is a group represented by the general formula CH ₂ = CRCONR'-, in which R is a hydrogen atom or a methyl group and R'is a hydrogen atom or an alkyl. It is the basis. Hydrogen atom is preferable because R has high sensitivity in photoradical polymerization and improves heat resistance and solvent resistance of the colored layer. Further, the R'is preferably a hydrogen atom from the viewpoint that the heat resistance and solvent resistance of the colored layer can be improved by forming a hydrogen bond and cross-linking more strongly.
The polymerizable functional group includes a (meth) acryloyl group and a (meth) acrylamide group because it has high sensitivity in photoradical polymerization and improves heat resistance and solvent resistance of the colored layer and pattern adhesion during alkaline development. At least one of the above is preferable, and from the viewpoint of solvent solubility, it is preferable to contain at least a (meth) acryloyl group.

As the phosphorus atom-containing polyfunctional monomer, a phosphorus atom-containing polyfunctional monomer having no acidic group is particularly preferable from the viewpoint of further improving solvent resistance. When it does not have an acidic group, it has a low affinity for a highly polar solvent such as NMP, and it is presumed that the penetration of the solvent can be further suppressed.
Further, as the phosphorus atom-containing polyfunctional monomer, (i) a phosphorus atom and a (meth) acrylamide group having a polyphosphoric acid ester structure in which two or more phosphorus atoms are bonded by an −O— bond are used. A phosphorus atom-containing polyfunctional monomer having at least one structure selected from containing and containing (iii) a phosphorus atom and an isocyanurate group is also preferred. When two or more phosphorus atoms have a polyphosphoric acid ester structure in which they are bonded by an -O- bond, the content of the phosphorus atom becomes large, so that the specific gravity becomes larger and the crosslinks are performed at high density or the polymerizability. Since it is possible to increase the number of functional groups, it is presumed that the permeation of the solvent can be further suppressed by performing the cross-linking reaction at a higher density. Further, when a (meth) acrylamide group is contained, a hydrogen bond is formed at the NH site and cross-linking is stronger, so that it is presumed that the penetration of the solvent can be further suppressed. Further, when an isocyanurate group is contained, the molecule becomes rigid and the solubility in a solvent such as NMP decreases due to the influence of the hydrophobicity of the isocyanurate group, so that the penetration of the solvent can be further suppressed. Is estimated to be.
Examples of these suitable phosphorus atom-containing polyfunctional monomers include those described in International Publication No. 2017/022790.

In the (E) polyfunctional monomer used in the colored resin composition of the present disclosure, the total content ratio of the phosphorus atom-containing polyfunctional monomer in the total amount of the (E) polyfunctional monomer is 20% by mass or more and 70% by mass or less. It is preferably 30% by mass or more and 60% by mass or less.

The content of the polyfunctional monomer (E) used in the colored resin composition of the present disclosure is not particularly limited, but the alkali is considered from the viewpoint of sufficiently advancing photocuring and suppressing elution of the exposed portion. It is preferably 5 parts by mass or more, and more preferably 20 parts by mass or more with respect to 100 parts by mass of the soluble resin. The content of the polyfunctional monomer (E) is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin from the viewpoint of improving alkali developability. Is.

In the colored resin composition of the present disclosure, the total content of the polyfunctional monomer (E) is preferably 5% by mass or more and 70% by mass or less in the total solid content of the colored resin composition, and is 10% by mass. It is more preferably 50% by mass or less.

The acid value of the phosphorus atom-containing monomer contained in the colored resin composition of the present disclosure is preferably 35 mgKOH / g or less, more preferably 20 mgKOH / g or less, and further 13 mgKOH / g or less. Is preferable. The phosphorus atom-containing monomer here includes not only polyfunctional (meth) acrylates having two or more (meth) acryloyl groups, but also (meth) acrylates having one (meth) acryloyl group.
The acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the phosphorus atom-containing monomer, and is measured by the method described in JIS K 0070. The value.
In the present disclosure, if the acid value of the phosphorus atom-containing monomer contained in the colored resin composition is too high, a salt is formed with a commonly used basic photoinitiator to generate agglomerated foreign matter in the colored resin composition. There is a fear. Further, if the acid value of the phosphorus atom-containing monomer as a whole is too high, the solubility in an alkaline developer becomes too high and it becomes difficult for a pattern to remain during development, or the crosslink density decreases, so that the solvent resistance is significantly deteriorated. There is a fear.
Even if it is a commercially available product, it is assumed that some acidic groups may remain during synthesis or some acidic groups may be generated during storage. However, if the acid value of the phosphorus atom-containing monomer is 35 mgKOH / g or less, the above Such a problem when the acid value is too high is suppressed, and it is suitable for the colored resin composition of the present disclosure.

[(F) Photoinitiator]
The photoinitiator used in the colored resin composition of the present disclosure is not particularly limited, and one or a combination of two or more of various conventionally known photoinitiators can be used. Specific examples include those described in International Publication No. 2012/144521.

The content of the photoinitiator used in the colored resin composition is preferably 0 with respect to 100 parts by mass of the polyfunctional monomer from the viewpoint of sufficiently causing a polymerization reaction and making the colored layer sufficiently hard. It is 0.01 part by mass or more, more preferably 5 parts by mass or more. Further, the content of the photoinitiator is set with respect to 100 parts by mass of the polyfunctional monomer from the viewpoint that the content of the coloring material or the like in the solid content of the colored resin composition is sufficient and a sufficient coloring concentration is obtained. It is preferably 100 parts by mass or less, and more preferably 60 parts by mass or less.

[Arbitrary additive component]
The colored resin composition of the present disclosure may contain various additives, if necessary, as long as the effects of the above-mentioned colored resin composition of the present disclosure are not impaired.

(Antioxidant)
It is preferable that the colored resin composition further contains an antioxidant from the viewpoint of heat resistance and light resistance. The antioxidant may be appropriately selected from conventionally known ones. Specific examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, phenothiazine-based antioxidants, and the like. From the viewpoint of heat resistance, it is preferable to use a hindered phenol-based antioxidant or a phenothiazine-based antioxidant.
The hindered phenolic antioxidant contains at least one phenol structure and has a structure in which at least one of the 2- and 6-positions of the hydroxyl group of the phenol structure is substituted with a substituent having 4 or more carbon atoms. It means an antioxidant. Further, it may be a latent antioxidant in which hindered phenol is latent as described in Japanese Patent Application Laid-Open No. 2015-132791.

When an antioxidant is used, the blending amount thereof is not particularly limited as long as the effect of the colored resin composition of the present disclosure is not impaired. The amount of the antioxidant to be blended is preferably 0.1% by mass or more, preferably 0.5% by mass or more, based on the total amount of solids in the colored resin composition from the viewpoint of excellent heat resistance. Is more preferable, and from the viewpoint that the colored resin composition can be made highly sensitive, it is preferably 5.0% by mass or less, preferably 4.0% by mass or less, based on the total amount of solids in the colored resin composition. Is more preferable.

(Other additives)
In addition to the above antioxidants, the additives include, for example, polymerization inhibitors, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters and the like. Can be mentioned.
Specific examples of the surfactant and the plasticizer include those described in Pamphlet No. 2012/144521 of International Publication No. 2012/144521.

<Mixing ratio of each component in the colored resin composition>
In the colored resin composition of the present disclosure, the total amount of (D) alkali-soluble resin, (E) polyfunctional monomer, and (F) photoinitiator as a binder component is based on the total solid content of the colored resin composition. From the viewpoint that a colored layer having sufficient hardness and adhesion to the substrate can be obtained, it is preferably 10% by mass or more, more preferably 30% by mass or more, and has excellent developability or heat. It is preferably 90% by mass or less, more preferably 80% by mass or less, from the viewpoint of suppressing the generation of fine wrinkles due to shrinkage.

The content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It is usually preferably in the range of 55% by mass or more and 95% by mass or less, particularly 65% by mass, from the viewpoint of excellent coatability with respect to the total amount of the colored resin composition containing the solvent. It is more preferably in the range of 88% by mass or less.

<Manufacturing method of colored resin composition>
The method for producing the colored resin composition of the present disclosure uses, if desired, a colorant dispersion liquid according to the present disclosure, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. Any method may be used as long as it contains various additive components and the coloring material can be uniformly dispersed in the solvent from the dispersant, and is not particularly limited, and can be prepared by mixing using a known mixing means. can.
Examples of the method for preparing the colored resin composition include (1) a binder component containing an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator in a color material dispersion, and various additive components used as desired. (2) A color material dispersion prepared by separately dispersing two or more kinds of color materials in a solvent together with a dispersant, or by dissolving the other color materials in a solvent without using a dispersant. And, in some cases, a method of mixing a binder component containing a coloring material solution, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and various additive components used as desired; (3) Color in a solvent. A method in which the material, the dispersant, the binder component, and various additive components used as desired are simultaneously added and mixed; (4) The dispersant, the binder component, and various additive components used as desired are added to the solvent. After adding and mixing, a method of adding a coloring material and mixing; and the like can be mentioned.
Among these methods, the method of preparing the color material dispersion liquid in advance according to the above (1) or (2) is preferable from the viewpoint of effectively preventing the color material from agglomerating and uniformly dispersing the color material.

4. Color filter The color filter according to the present disclosure is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and is a colored layer which is a cured product of the colored resin composition according to the present disclosure. Have.
Further, the method for manufacturing a color filter of the present disclosure is a method for manufacturing a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate.
It has a step of forming at least one of the colored layers by curing the colored resin composition according to the present disclosure.

Such a color filter according to the present disclosure will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present disclosure. According to FIG. 1, the color filter 10 of the present disclosure has a transparent substrate 1, a light-shielding portion 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present disclosure is a cured product of the colored resin composition according to the present disclosure.
The colored layer is usually formed in the opening of a light-shielding portion on a transparent substrate, which will be described later, and is usually composed of a colored pattern of three or more colors.
The arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type. Further, the width, area and the like of the colored layer can be arbitrarily set.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and the viscosity of the colored resin composition, etc., but is usually preferably in the range of 1 μm or more and 5 μm or less.

The colored layer can be formed by the following method.
First, the colored resin composition is applied onto a transparent substrate described later using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, a slit coating method, and a die coating method. , Form a wet coating.
Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to the wet coating film through a mask having a predetermined pattern to cause a photopolymerization reaction of an alkali-soluble resin, a polyfunctional monomer, or the like. Use a photosensitive 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.
In addition, heat treatment may be performed in order to accelerate the polymerization reaction after exposure. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, a coating film is formed in a desired pattern by developing with a developing solution to dissolve and remove the unexposed portion. As the developing solution, a solution in which an alkali is usually dissolved in water or a water-soluble solvent is used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as a developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. After the development treatment, a heat treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited and are appropriately selected depending on the intended use of the coating film.

(Shading part)
The light-shielding portion in the color filter of the present disclosure is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light-shielding portion is not particularly limited, and examples thereof include a striped shape and a matrix shape. Examples of the light-shielding portion include a black pigment dispersed or dissolved in a binder resin, a metal thin film such as chromium and chromium oxide, and the like. This metal thin film may be a CrO _x film (x is an arbitrary number) and a Cr film in which two layers are laminated, or a CrO _x film having a further reduced reflectance (x is an arbitrary number). , CrN _y film (y is an arbitrary number) and Cr film may be laminated in three layers.
When the light-shielding portion is a black color material dispersed or dissolved in a binder resin, the method for forming the light-shielding portion is not particularly limited as long as the light-shielding portion can be patterned. For example, a photolithography method, a printing method, an inkjet method, etc. using a colored resin composition for a light-shielding portion can be mentioned.

The film thickness of the light-shielding portion is set to about 0.2 μm or more and 0.4 μm or less in the case of a metal thin film, and 0.5 μm or more and 2 μm or less in the case of a black color material dispersed or dissolved in a binder resin. Set by degree.

(Transparent board)
The transparent substrate in the color filter of the present disclosure may be a substrate that is transparent to visible light, and is not particularly limited, and a transparent substrate used in a general color filter can be used. Specifically, it has flexibility and flexibility such as inflexible transparent rigid material such as quartz glass, non-alkali glass, and synthetic quartz plate, or transparent resin film, optical resin plate, and flexible glass. A transparent flexible material can be mentioned.
The thickness of the transparent substrate is not particularly limited, but for example, one having a thickness of 50 μm or more and 1 mm or less can be used depending on the use of the color filter of the present disclosure.
In addition to the transparent substrate, light-shielding portion, and colored layer, the color filter of the present disclosure forms, for example, an overcoat layer, a transparent electrode layer, an alignment film for aligning a liquid crystal material, a columnar spacer, and the like. It may be the one that has been done. The color filter of the present disclosure is not limited to the above-exemplified configuration, and a known configuration generally used for a color filter can be appropriately selected and used.

5. Liquid Crystal Display Device The liquid crystal display device of the present disclosure includes the color filter according to the present disclosure described above, an opposing substrate, and a liquid crystal layer located between the color filter and the opposing substrate.
Such a liquid crystal display device of the present disclosure 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 disclosure. As illustrated in FIG. 2, the liquid crystal display device 40 of the present disclosure includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer 15 located between the color filter 10 and the counter substrate 20. And have. In FIG. 2, an example in which the alignment film 13a is located on the colored layer 3 side of the color filter 10 and the alignment film 13b is located on the opposite substrate 20 side, and the liquid crystal layer 15 is located between the two alignment films 13a and 13b. Is shown. Further, in FIG. 2, the liquid crystal display device 40 is located on the facing substrate 20 side of the liquid crystal display device 40 with the polarizing plate 25a located outside the color filter 10 and the polarizing plate 25b located outside the facing substrate 20. An example of having a backlight 30 located outside the positioned polarizing plate 25b is shown.
The liquid crystal display device of the present disclosure is not limited to the configuration shown in FIG. 2, and can be generally known as a liquid crystal display device using a color filter.

The drive system of the liquid crystal display device of the present disclosure is not particularly limited, and a drive system generally used for a liquid crystal display device can be adopted. Examples of such a drive system include a TN system, an IPS system, an OCB system, an MVA system, and the like. In the present disclosure, any of these methods can be preferably used.
Further, as the facing substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present disclosure and the like.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used depending on the driving method of the liquid crystal display device of the present disclosure.

As a method for forming the liquid crystal layer, a method generally used as a method for producing 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 an opposing substrate, the liquid crystal is heated to form an isotropic liquid, and the liquid crystal is made into the liquid crystal cell by using the capillary effect. The liquid crystal layer can be formed by injecting in the state of the above and sealing with an adhesive. After that, the enclosed liquid crystal can be oriented 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 liquid crystal layer can be formed by superimposing the color filter and the opposing substrate under reduced pressure and adhering them with the sealant. After that, the enclosed liquid crystal can be oriented by slowly cooling the liquid crystal cell to room temperature.

Further, as the backlight used in the liquid crystal display device of the present disclosure, it can be appropriately selected and used according to the use of the liquid crystal display device. As the backlight, for example, in addition to a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp), a backlight unit using a white LED or a white organic EL as a light source can be provided.
Examples of the white LED include a white LED that obtains white light by mixing colors by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by combining a blue LED, a red LED, and a green phosphor, and a blue LED. A white LED that obtains white light by mixing colors with a red light emitting phosphor and a green light emitting phosphor, a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor, an ultraviolet LED, a red light emitting phosphor, and a green light emitting fluorescence Examples thereof include a white LED that obtains white light by mixing colors by combining a body and a blue light emitting phosphor. Quantum dots may be used as the phosphor.

6. Light-emitting display device The light-emitting display device according to the present disclosure includes the above-mentioned color filter according to the present disclosure and a light emitting body. Examples of the light emitting display device according to the present disclosure include an organic light emitting display device having an organic light emitting body as the light emitting body. The luminescent material is not limited to the organic luminescent material, and an inorganic luminescent material can be used as appropriate.
Such a light emitting display device of the present disclosure will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of the light emission display device of the present disclosure. As illustrated in FIG. 3, the light emitting display device 100 of the present disclosure includes a color filter 10 and a light emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the light emitting body 80.

As a method of laminating the light emitting body 80, for example, a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter. Alternatively, a method of bonding the light emitter 80 formed on another substrate onto the inorganic oxide film 60 and the like can be mentioned. 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 of the light emitting body 80, known ones can be appropriately used. The light emitting display device 100 produced in this manner can be applied to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
The light emitting display device of the present disclosure is not limited to the light emitting display device having the configuration shown in FIG. 3, and can be generally known as a light emitting display device using a color filter. ..

Hereinafter, the present disclosure will be specifically described with reference to examples. These statements do not limit this disclosure.

(Example 1)
(1) Synthesis of macromonomer MM-1 80.0 parts by mass of PGMEA was charged into a reactor equipped with a cooling tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream. , The temperature was heated to 100 ° C. 40.0 parts by mass of methyl methacrylate, 10.0 parts by mass of -t-butyl methacrylate, 15.0 parts by mass of -n-butyl methacrylate, 15.0 parts by mass of benzyl methacrylate, 2-ethoxyethyl methacrylate 20. A mixed solution of 0 parts by mass, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, and 1.30 parts by mass of α, α'-azobisisobutyronitrile (AIBN) was added dropwise over 1.0 hour. The mixture was further heated and stirred for 3 hours. Next, the nitrogen flow was stopped, the reaction solution was cooled to 80 ° C., and dry air was blown into the reaction solution. 0.10 parts by mass of methoxyphenol and 10 parts by mass of PGMEA were added and heated and stirred for 3 hours to obtain a 53.7% by mass solution of macromonomer MM-1. When the obtained macromonomer MM-1 was confirmed by GPC under the conditions of NMP, 0.01 mol / L lithium bromide addition / polystyrene standard, the weight average molecular weight (Mw) was 3400 and the number average molecular weight (Mn) was 1500. , The molecular weight distribution (Mw / Mn) was 2.27.

(2) Synthesis of Graft Copolymer A A reactor equipped with a cooling tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer was charged with 189.0 parts by mass of PGMEA, and while stirring under a nitrogen stream, It was heated to a temperature of 90 ° C. 142.2 parts by mass (solid content 66.7 parts by mass), 33.3 parts by mass of glycidyl methacrylate (abbreviated as GMA), 2.50 parts by mass of n-dodecyl mercaptan, 53.6 parts by mass of PGMEA. , A mixed solution of 1.0 part by mass of AIBN was added dropwise over 1.5 hours, heated and stirred for 3 hours, and then a mixed solution of 0.10 part by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes. Stirring at warm for 1 hour gave a 25.2% by weight solution of graft copolymer A. As a result of GPC measurement, the obtained graft copolymer A had a weight average molecular weight (Mw) of 11900, a number average molecular weight (Mn) of 6700, and a molecular weight distribution (Mw / Mn) of 1.78.

(3) Production of Polymer Dispersant A In a reactor, 100.0 parts by mass of the graft copolymer A, 27.80 parts by mass of PGMEA, and 9.27 parts by mass of phenylphosphonic acid (trade name: "PPA" manufactured by Nissan Chemical Co., Ltd.) (1 mol equivalent to GMA of graft copolymer A) was charged and stirred at 90 ° C. for 2 hours to obtain a polymer dispersant A solution (solid content 25.0% by mass). The progress of the esterification reaction between GMA and PPA of the graft copolymer A ^{was confirmed by acid value measurement and 1} H-NMR measurement (confirmation that the peak derived from the epoxy group disappeared).
As a result of GPC measurement, the obtained polymer dispersant A had a weight average molecular weight (Mw) of 53600, a number average molecular weight (Mn) of 12500, and a molecular weight distribution (Mw / Mn) of 4.29. The acid value of the obtained polymer dispersant A was 144.3 mgKOH / g.
Further, using a thermogravimetric analyzer (trade name: "DTG-60A" manufactured by Shimadzu Corporation), the temperature rise rate of 6 mg of the polymer dispersant A sample was set to 10 ° C./min, and the temperature was changed from room temperature (23 ° C.) to 230 ° C. When the temperature was raised to 230 ° C. and the weight change was measured for 30 minutes in a nitrogen atmosphere, a weight loss derived from the t-butyl group was confirmed.

(Example 2)
(1) Synthesis of macromonomer MM-2 In the synthesis of macromonomer MM-1, macromonomer MM was changed to 20.0 parts by mass of methyl methacrylate and 30.0 parts by mass of -t-butyl methacrylate. A 52.5% by mass solution of macromonomer MM-2 was obtained in the same manner as in the synthesis of -1. As a result of GPC measurement, the obtained macromonomer MM-2 had a weight average molecular weight (Mw) of 3600, a number average molecular weight (Mn) of 1500, and a molecular weight distribution (Mw / Mn) of 2.40.

(2) Synthesis of Graft Copolymer B In the synthesis of the graft copolymer A, 127.0 parts by mass (solid content 66.) Of the macromonomer MM-2 solution obtained above was used instead of the macromonomer MM-1 solution. A 25.2% by mass solution of the graft copolymer B was obtained in the same manner as in the synthesis of the graft copolymer A except that 7% by mass) was used. As a result of GPC measurement, the obtained graft copolymer B had a weight average molecular weight (Mw) of 11300, a number average molecular weight (Mn) of 6300, and a molecular weight distribution (Mw / Mn) of 1.79.

(3) Production of Polymer Dispersant B In the synthesis of the polymer dispersant A, the polymer dispersant A is used except that the graft copolymer B obtained above is used instead of the graft copolymer A. A 25.0% by mass solution of the polymer dispersant B was obtained in the same manner as in the synthesis. The progress of the esterification reaction between GMA and PPA of the graft copolymer B ^{was confirmed by acid value measurement and 1} H-NMR measurement (confirmation that the peak derived from the epoxy group disappeared).
As a result of GPC measurement, the obtained polymer dispersant B had a weight average molecular weight (Mw) of 55300, a number average molecular weight (Mn) of 14100, and a molecular weight distribution (Mw / Mn) of 3.92. The acid value of the obtained polymer dispersant B was 163.7 mgKOH / g.
Moreover, when the weight change was measured using DTG-60A in the same manner as in the graft copolymer A, a weight loss derived from the t-butyl group was confirmed.

(Example 3)
(1) Synthesis of macromonomer MM-3 In the synthesis of macromonomer MM-1, macromonomer MM- was used except that -t-butyl methacrylate was changed to 50.0 parts by mass without adding methyl methacrylate. A 53.0% by mass solution of macromonomer MM-3 was obtained in the same manner as in the synthesis of 1. As a result of GPC measurement, the obtained macromonomer MM-3 had a weight average molecular weight (Mw) of 4100, a number average molecular weight (Mn) of 1700, and a molecular weight distribution (Mw / Mn) of 2.32.

(2) Synthesis of Graft Copolymer C In the synthesis of the graft copolymer A, 125.8 parts by mass (solid content 66.) Of the macromonomer MM-3 solution obtained above was used instead of the macromonomer MM-1 solution. A 25.8% by mass solution of the graft copolymer C was obtained in the same manner as in the synthesis of the graft copolymer A except that 7% by mass) was used. As a result of GPC measurement, the obtained graft copolymer C had a weight average molecular weight (Mw) of 10300, a number average molecular weight (Mn) of 4600, and a molecular weight distribution (Mw / Mn) of 2.24.

(3) Production of Polymer Dispersant C In the synthesis of the polymer dispersant A, except that the graft copolymer C obtained above was used instead of the graft copolymer A, the polymer dispersant A was used. A 25.0% by mass solution of the polymer dispersant C was obtained in the same manner as in the synthesis. The progress of the esterification reaction between GMA and PPA of the graft copolymer C ^{was confirmed by acid value measurement and 1} H-NMR measurement (confirmation that the peak derived from the epoxy group disappeared).
As a result of GPC measurement, the obtained polymer dispersant C had a weight average molecular weight (Mw) of 65200, a number average molecular weight (Mn) of 12900, and a molecular weight distribution (Mw / Mn) of 5.05. The acid value of the obtained polymer dispersant C was 156.6 mgKOH / g.
Moreover, when the weight change was measured using DTG-60A in the same manner as in the graft copolymer A, a weight loss derived from the t-butyl group was confirmed.

(Example 4)
(1) Synthesis of Macromonomer MM-4 In the synthesis of macromonomer MM-1, methyl methacrylate, -n-butyl methacrylate, benzyl methacrylate, and 2-ethoxyethyl methacrylate were not added, and methacrylic acid-t was added. A 50.1 mass% solution of macromonomer MM-4 was obtained in the same manner as in the synthesis of macromonomer MM-1, except that −butyl was changed to 100.0 parts by mass. As a result of GPC measurement, the obtained macromonomer MM-4 had a weight average molecular weight (Mw) of 3600, a number average molecular weight (Mn) of 1500, and a molecular weight distribution (Mw / Mn) of 2.35.

(2) Synthesis of Graft Copolymer D In the synthesis of the graft copolymer A, 130.8 parts by mass of the macromonomer MM-4 solution obtained above (effective solid content 66) was used instead of the macromonomer MM-1 solution. A 26.3% by mass solution of the graft copolymer D was obtained in the same manner as in the synthesis of the graft copolymer A except that 0.7 parts by mass) was used. As a result of GPC measurement, the obtained graft copolymer D had a weight average molecular weight (Mw) of 11800, a number average molecular weight (Mn) of 5200, and a molecular weight distribution (Mw / Mn) of 2.27.

(3) Production of Polymer Dispersant D In the synthesis of the polymer dispersant A, except that the graft copolymer D obtained above was used instead of the graft copolymer A, the polymer dispersant A was used. A 25.0 mass% solution of the polymer dispersant D was obtained in the same manner as in the synthesis. The progress of the esterification reaction between GMA and PPA of the graft copolymer D ^{was confirmed by acid value measurement and 1} H-NMR measurement (confirmation that the peak derived from the epoxy group disappeared).
As a result of GPC measurement, the obtained polymer dispersant D had a weight average molecular weight (Mw) of 77300, a number average molecular weight (Mn) of 16900, and a molecular weight distribution (Mw / Mn) of 4.57. The acid value of the obtained polymer dispersant D was 166.5 mgKOH / g.
Moreover, when the weight change was measured using DTG-60A in the same manner as in the graft copolymer A, a weight loss derived from the t-butyl group was confirmed.

(Comparative Example 1)
(1) Synthesis of macromonomer MM-5 In the synthesis of macromonomer MM-1, macromonomer MM was added except that the amount of methyl methacrylate was changed to 50.0 parts by mass and -t-butyl methacrylate was not added. A 48.7% by mass solution of macromonomer MM-5 was obtained in the same manner as in the synthesis of -1. As a result of GPC measurement, the obtained macromonomer MM-5 had a weight average molecular weight (Mw) of 4000, a number average molecular weight (Mn) of 1900, and a molecular weight distribution (Mw / Mn) of 2.11.

(2) Synthesis of Graft Copolymer E In the synthesis of the graft copolymer A, 137.0 parts by mass (solid content 66.) Of the macromonomer MM-5 solution obtained above was used instead of the macromonomer MM-1 solution. A 26.0% by mass solution of the graft copolymer E was obtained in the same manner as in the synthesis of the graft copolymer A except that 7% by mass) was used. As a result of GPC measurement, the obtained graft copolymer E had a weight average molecular weight (Mw) of 13300, a number average molecular weight (Mn) of 5000, and a molecular weight distribution (Mw / Mn) of 2.66.

(3) Production of Comparative Polymer Dispersant E In the synthesis of the polymer dispersant A, the polymer dispersant A is used except that the graft copolymer E obtained above is used instead of the graft copolymer A. A 25.0% by mass solution of the comparative polymer dispersant E was obtained in the same manner as in the above synthesis. The progress of the esterification reaction between GMA and PPA of the graft copolymer E ^{was confirmed by acid value measurement and 1} H-NMR measurement (confirmation that the peak derived from the epoxy group disappeared).
As a result of GPC measurement, the obtained comparative polymer dispersant E had a weight average molecular weight (Mw) of 60100, a number average molecular weight (Mn) of 16700, and a molecular weight distribution (Mw / Mn) of 3.60. The acid value of the obtained comparative polymer dispersant E was 142.7 mgKOH / g.

Here, each abbreviation in the table is as follows.
tBMA: Methacrylic acid-t-butyl MMA: Methyl methacrylate (Tgi = 105 ° C)
BzMA: Benzyl methacrylate (Tgi = 54 ° C)
nBMA: Methacrylic acid-n-butyl (Tgi = 20 ° C)
EEMA: 2-ethoxyethyl methacrylate (Tgi = -16 ° C)
GMA: Glycydyl methacrylate PPA: Phenylphosphonic acid

(evaluation)
<Measurement of infrared absorption spectrum>
The polymer dispersants A to D and the comparative polymer dispersants E are diluted with PGMEA or propylene glycol monomethyl ether so that the solid content concentration of the copolymer is 10% by mass or more and 20% by mass or less, respectively. , Diluted solution was obtained. The obtained diluted solution was applied onto a transparent glass substrate and dried to form a coating film so that the film thickness after heating at 230 ° C. for 20 minutes was 2.00 μm ± 0.5 μm. The infrared absorption spectrum (IR spectrum) of this coating film was measured before and after heating at 230 ° C. for 20 minutes. An FT / IR-6100 manufactured by JASCO Corporation was used as the IR spectrum measuring device.
Table 2 shows the values of ^{the peaks around 2980 cm -1} derived from the t-butyl group and the peaks of 1760 ± 5 cm ^{-1 derived from the acid anhydride group before and after heating in each copolymer. For the values shown in Table 2, the peak having the maximum value at 1450 ± 10 cm -1} derived from the methylene group of the main chain in each copolymer was set as the reference peak, and the peak intensity before and after heating of the reference peak was set to 1. The value of time.
Further, as an example of the result of the IR spectrum, the IR spectrum of the polymer dispersant D of Example 4 is shown in FIG. 4, and a partially enlarged view thereof is shown in FIG. Further, the IR spectrum of the comparative polymer dispersant E of Comparative Example 1 is shown in FIG. 6, and a partially enlarged view thereof is shown in FIG. 7. In FIGS. 4 to 7, the IR spectrum before heating (before baking) is shown by a solid line, and the IR spectrum after heating (after baking) is shown by a dotted line.
The polymer dispersants A to D obtained in each of the examples shown in Table 2 had a decrease in peak intensity around ^{2980 cm-1} derived from the t-butyl group before and after heating at 230 ° C. for 20 minutes, and were acid anhydrides. The peak intensity of 1760 ± 5 cm ^-1 derived from the group increased, and the intensity was 0.35 or more.
On the other hand, it was confirmed that the comparative polymer dispersant E obtained in Comparative Example had a decrease in peak intensity derived from at least one of a hydrocarbon group and a hydrocarbon group-substituted silyl group before and after heating at 230 ° C. for 20 minutes. There wasn't. ^{Furthermore, no peak with an inflection point was observed at 1760 ± 5 cm -1} derived from the acid anhydride group before and after heating at 230 ° C. for 20 minutes, and 1760 ± 5 cm before and after heating at 230 ° C. for 20 minutes. ^No increase was confirmed in the peak intensity of -1.

(Synthesis example 1: Synthesis of blue color material α)
(1) Synthesis of Intermediate 1 With reference to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 parts by mass of Intermediate 1 represented by the following chemical formula (1) is added. (Yield 70%) was obtained.
It was confirmed from the following analysis results that the obtained compound was the target compound.
-MS (ESI) (m / z): 511 (+), divalent / elemental analysis value: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (7)
8.06%, 7.75%, 7.69%)
The thermal decomposition temperature of the obtained compound was measured by DTG-60A manufactured by Shimadzu Corporation and determined from the intersection of tangent lines near the weight loss temperature, and was found to be 239 ° C.

(2) Synthesis of Blue Color Material α 15.00 parts by mass of the intermediate was added to 300 parts by mass of water and dissolved at 90 ° C. to prepare 1 solution of the intermediate. Next, add 10.44 parts by mass of phosphotungstic acid, n-hydrate H ₃ [PW ₁₂ O ₄₀ ], nH ₂ O (n = 30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) to 100 parts by mass of water, and at 90 ° C. Stirring was performed to prepare an aqueous solution of phosphotungstic acid. The aqueous solution of phosphotungstic acid prepared in the above 1 solution of the intermediate was mixed at 90 ° C., and the produced precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 parts by mass of a blue color material α, which is a metal lake color material of a triarylmethane-based basic dye represented by the following chemical formula (2).
It was confirmed from the following analysis results that the obtained compound was the target compound.
-MS (ESI) (m / z): 510 (+), divalent / elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) 5.17%, 4.11%)

(Synthesis Example 2: Synthesis of Binder Resin A)
In a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 120 parts by mass of PGMEA was charged as a solvent, the temperature was raised to 90 ° C. in a nitrogen atmosphere, and then 32 parts by mass of methyl methacrylate. A mixture containing 22 parts by mass of cyclohexyl methacrylate, 24 parts by mass of methacrylate, 2.0 parts by mass of AIBN as an initiator and 4.5 parts by mass of n-dodecyl mercaptan as a chain transfer agent was continuously added over 1.5 hours. Dropped in.
Then, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropping.
Next, while blowing air, 22 parts by mass of glycidyl methacrylate was added, the temperature was raised to 110 ° C., 0.2 part by mass of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours. Solid content 45% by mass) was obtained.
The obtained binder resin A had a weight average molecular weight (Mw) of 8900, a number average molecular weight (Mn) of 4200, a molecular weight distribution (Mw / Mn) of 2.11 and an acid value of 78 mgKOH / g.

(Preparation Example 1: Preparation of Binder Composition A)
20.22 parts by mass of PGMEA, 17.78 parts by mass of binder resin A (solid content 45% by mass) of Synthesis Example 2, 5 to 6 functional acrylate monomers (trade name: Aronix M402, manufactured by Toa Synthetic) 8.00 parts by mass, 2 -Methyl-1 [4- (methylthio) phenyl] -2-morifolinopropane-1-one (trade name: Irgacure907, manufactured by BASF) 3.00 parts by mass, 2,4 diethylthioxanthone (trade name: Kayacure DETX-S) , Nippon Kayaku Co., Ltd.) 1.00 parts by mass was mixed to prepare a binder composition A (solid content 40% by mass).

(Preparation Example 2: Preparation of Binder Composition B)
44.36 parts by mass of PGMEA, 28.44 parts by mass of binder resin A (solid content 45% by mass) of Synthesis Example 2, phosphorus atom-containing polyfunctional (meth) acrylate (trade name: Viscote # 3PA, manufactured by Osaka Organic Chemical Industry Co., Ltd., acid ^{When confirmed by 31} P-NMR measurement with a valence of 5 mgKOH / g, a phosphate triester was the main component, a trace amount of phosphate diester was detected, and the peak integration ratio of the phosphate triester was 95% or more.) Binder composition by mixing 12.80 parts by mass, polyfunctional acrylate monomer (trade name: Aronix M402, manufactured by Toa Synthetic) 6.40 parts by mass, Irgacure907 6.00 parts by mass, and Kayacure DETX-S 2.00 parts by mass. B (solid content 40% by mass) was prepared.

(Example 5)
(1) Preparation of Color Material Dispersion Solution As a color material, 10.00 parts by mass of the blue color material α of Synthesis Example 1 and 20.0 parts by mass of the polymer dispersant A solution (solid content 5.00% by mass), Synthesis Example 2. Binder resin A 6.67 parts by mass (solid content 3.00% by mass) and PGMEA 63.33 parts by mass were mixed and pre-dispersed with a paint shaker (manufactured by Asada Iron Works) for 1 hour with 2 mm zirconia beads. The dispersion was carried out with 0.1 mm zirconia beads for 4 hours to obtain a color material dispersion solution.
(2) Preparation of Colored Resin Composition 41.70 parts by mass of the obtained color material dispersion liquid, 24.24 parts by mass of the binder composition A of Preparation Example 1, 34.01 parts by mass of PGMEA, and a surfactant R08MH (manufactured by DIC). 0.05 parts by mass was added and mixed, and pressure filtration was performed to obtain a colored resin composition.

(Examples 6 to 8, Comparative Example 2)
(1) Preparation of Color Material Dispersion Liquid In the preparation of the color material dispersion liquid of Example 5, the dispersant solution containing the dispersant shown in Table 3 was used instead of the polymer dispersant A solution. A color material dispersion was obtained in the same manner as in Example 5.
(2) Preparation of Colored Resin Composition The colored resin composition of Example 5 except that the above-mentioned colorant dispersion containing the dispersant shown in Table 3 was used in the preparation of the colored resin composition of Example 5. A colored resin composition was obtained in the same manner as the preparation.

(evaluation)
<Color material dispersion stability>
As an evaluation of the color material dispersion stability, the blue color material dispersions obtained in Examples and Comparative Examples shown in Table 3 were allowed to stand at 40 ° C. for 1 week, and the colors in the above color material dispersion before and after the standing were allowed to stand. The average particle size and shear viscosity of the material particles were measured. The "Nanotrack Particle Size Distribution Meter UPA-EX150" manufactured by Microtrac Bell is used for measuring the average particle size, and the "Rheometer MCR301" manufactured by Antonio Par is used for measuring the viscosity, and the shear viscosity when the shear rate is 60 rpm. Was measured. The results are shown in Table 3.

<Optical performance evaluation, heat resistance evaluation>
The colored resin compositions obtained in Examples and Comparative Examples shown in Table 3 were applied onto a glass substrate (manufactured by Nippon Electric Glass Co., Ltd., “OA-10G”) having a thickness of 0.7 mm using a spin coater. Then, it was heated and dried on a hot plate at 80 ° C. for 3 minutes. A cured film was obtained by irradiating with ultraviolet rays of ^{40 mJ / cm 2} using an ultra-high pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity y = 0.082, and the chromaticity (x, y), brightness (Y), L, a, b (L _{0) of the obtained colored substrate were obtained.} , A ₀ , b ₀ ) were measured using an Olympus "microscopic differential light measuring device OSP-SP200".
The above colored substrate was post-baked in a clean oven at 230 ° C. for 60 minutes, and the contrast and chromaticity (x, y), luminance (Y) and L, a, b (L ₁ , a _{1) of the obtained colored film were obtained.} , B ₁ ) was measured. A "contrast tester CT-1B" manufactured by Tsubosaka Electric was used to measure the contrast.
Further, the above-mentioned colored substrate was subjected to a second post-baking treatment in a clean oven at 230 ° C. for 30 minutes, and the chromaticity (x, y), brightness (Y) and L, a, b (L) of the obtained colored film were obtained. _{2, a 2, b 2)} was measured.
As a heat resistance evaluation, the color difference (ΔEab) after the second post-baking and after the first post-baking was calculated from the following formula.
ΔEab = {(L _2- L ₁ ) ² + (a _2- a ₁ ) ² + (b _2- b ₁ ) ² } ^1/2
As a result of the optical performance evaluation, the chromaticity (x, y), brightness (Y), film thickness, and contrast of the colored film after the first post-baking treatment are shown in Tables 3 and 5. As a result of the heat resistance evaluation, the results of the chromaticity (x, y), the brightness (Y), and the color difference (ΔEab) of the colored film after the second post-baking treatment are shown in Tables 4 and 6.

(Summary of results)
As shown in Tables 3 and 4, the colored layer of the example formed by using the polymer dispersant of the present disclosure has higher brightness than that of the comparative example, and the color before and after the second post-baking. The degree change was small and the film was made thinner. Further, in the examples, the higher the content ratio of the t-butyl group and the stronger the IR peak intensity derived from the acid anhydride group after heating, the more heat resistant the obtained colored layer becomes. It was revealed that it was high, bright, and thinned.

(Examples 9 to 11, Comparative Example 3)
(1) Preparation of Color Material Dispersion Liquid In the preparation of the color material dispersion liquid of Example 5, the dispersant solution containing the dispersant shown in Table 5 was used instead of the polymer dispersant A solution. A color material dispersion was obtained in the same manner as in Example 5.
(2) Preparation of Colored Resin Composition 41.70 parts by mass of the above-mentioned color material dispersion liquid, 24.24 parts by mass of the binder composition B of Preparation Example 2, 34.01 parts by mass of PGMEA, and a surfactant R08MH (DIC). (Manufactured by) 0.05 parts by mass was added and mixed, and pressure filtration was performed to obtain a colored resin composition.

(Summary of results)
As shown in Tables 5 and 6, the colored layer of the example formed by using the polymer dispersant of the present disclosure has higher brightness than that of the comparative example, and the color before and after the second post-baking. The degree change was small and the film was made thinner. Further, in the examples, the higher the content ratio of the t-butyl group and the stronger the IR peak intensity derived from the acid anhydride group after heating, the more heat resistant the obtained colored layer becomes. It was clarified that it was high, bright, and thinned. Further, comparing Table 4 and Table 6, when the polyfunctional monomer contains a phosphorus atom-containing polyfunctional monomer, the change in chromaticity before and after the second post-bake is further reduced, and the brightness is higher. , It was clarified that the film was made thinner.

(Example 12)
(1) Preparation of Color Material Dispersion Liquid As a color material, 10.00 parts by mass of the blue color material α of Synthesis Example 1 and 16.00 parts by mass of the polymer dispersant B solution (solid content: 4.00 parts by mass) were synthesized. Example 2 binder resin A 8.89 parts by mass (solid content 4.00 parts by mass) and PGMEA 65.11 parts by mass were mixed and pre-dispersed with a paint shaker (manufactured by Asada Iron Works) for 1 hour with 2 mm zirconia beads. Further, the main dispersion was dispersed with 0.1 mm zirconia beads for 4 hours to obtain a color material dispersion liquid.
(2) Preparation of Colored Resin Composition 42.86 parts by mass of the obtained color material dispersion liquid, 41.63 parts by mass of the binder composition B of Preparation Example 2, 15.46 parts by mass of PGMEA, and a surfactant R08MH (manufactured by DIC). ) 0.05 parts by mass was added and mixed, and pressure filtration was performed to obtain a colored resin composition.

(Comparative Example 4)
Block copolymer containing 60.74 parts by mass of PGMEA and a tertiary amino group (trade name: BYK-LPN6919, manufactured by Big Chemie) (amine value 120 mgKOH / g, solid content 60% by mass) 35.64 parts by mass ( 21.38 parts by mass of solid content), 3.62 parts by mass of PPA (0.5 mol equivalent to the tertiary amino group of block copolymer), and stirring at 40 ° C. for 30 minutes to make the comparison higher. A molecular dispersant F (solid content 25% by mass) was prepared.
In Example 12, the comparative polymer dispersant F solution was used in the same manner as in Example 12 except that 16.00 parts by mass (solid content: 4.00 parts by mass) of the comparative polymer dispersant F solution was used instead of the polymer dispersant B solution. A colored material dispersion and a colored resin composition of Comparative Example 4 were obtained.
(Comparative Example 5)
In Comparative Example 4, the colorant dispersion and the colored resin composition of Comparative Example 5 were obtained in the same manner as in Comparative Example 4 except that the binder resin composition A was used instead of the binder composition B.

<Optical performance evaluation>
In the colored resin compositions obtained in Examples and Comparative Examples shown in Table 7, optical performance evaluation and heat resistance evaluation were performed in the same manner as in Example 5.
As a result, Table 7 shows the results of the chromaticity (x, y), brightness (Y), film thickness, contrast, and color difference (ΔEab) of the heat resistance evaluation of the colored film after the first post-baking treatment.

<Solvent resistance evaluation>
In the colored resin compositions obtained in Examples and Comparative Examples shown in Table 7, the colored film after the post-baking treatment obtained in the above optical performance and heat resistance evaluation was cross-cut into 100 squares at 1 mm intervals by a cutter. Then, it was placed on a hot plate at 80 degrees, NMP was dropped on the cross-cut surface, and the mixture was allowed to stand for 20 minutes, and the presence or absence of peeling of the colored film was visually confirmed.
(Solvent resistance evaluation standard)
A: No change.
B: The film surface is peeled off.

<Solvent resolubility evaluation>
The colored resin compositions obtained in Examples and Comparative Examples shown in Table 7 were applied to the surface of a glass substrate (100 mm × 5 mm × 0.7 mm) by dip coating, and 30 at a temperature of 23 ° C. and a humidity of 80% RH. It was dried by leaving it for a minute to form a dry coating film. The obtained glass test piece (dry coating film) was immersed in PGMEA and stirred for 15 seconds to redissolve the dry coating film. The state of re-dissolution of the dry coating film was visually confirmed, and the solvent re-solubility was evaluated according to the following evaluation criteria.
(Solvent resolubility evaluation standard)
A: Dissolves in PGMEA without exfoliation.
B: Peeled pieces remain or do not dissolve in PGMEA.

<Evaluation of adhesion to the substrate>
In the colored resin compositions obtained in the examples and comparative examples shown in Table 7, the colored film after the first post-baking treatment obtained in the above-mentioned optical performance evaluation and heat resistance evaluation is based on JIS K5600. Then, a cross-cut tape peeling test was conducted, and the adhesion was evaluated according to the following evaluation criteria.
(Adhesion evaluation criteria)
A: Cross-cut grid-shaped eyes remain.
B: The film itself peels off.

(Summary of results)
As shown in Table 7, the colored layer of Example 12 formed by using the polymer dispersant of the present disclosure further suppresses the change in chromaticity after high-temperature heating by combining with a phosphorus atom-containing polyfunctional monomer. However, it was also excellent in adhesion to the substrate, solvent resistance, and solvent resolubility. In Comparative Example 4, since the colored layer was a combination of the comparative polymer dispersant F and the phosphorus atom-containing polyfunctional monomer, the chromaticity change after high-temperature heating was carried out even if the phosphorus atom-containing polyfunctional monomer was contained. It was larger than that of the above, and further, the adhesion to the substrate was inferior. In Comparative Example 5, since the colored layer was a combination of the comparative polymer dispersant F and a polyfunctional monomer containing no phosphorus atom, the change in chromaticity after heating at a high temperature was larger than that in the example, and the solvent resistance was large. The sex was also significantly inferior to that of the examples.

1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 13a, 13b Alignment film 15 Liquid crystal layer 20 Opposing substrate 25a, 25b Polarizing plate 30 Backlight 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 Light emitter 100 Light emitting display device

Claims (11)

A block having at least one selected from the structural unit represented by the following general formula (I) and the structural unit represented by the following general formula (I'), and the structural unit represented by the following general formula (II). It is a polymer, or at least one selected from the structural unit represented by the following general formula (I) and the structural unit represented by the following general formula (I'), and the configuration represented by the following general formula (III). It is a graft copolymer having a unit and
Before and after heating at 230 ° C. for 5 minutes or more, the peak intensity derived from at least one of the hydrocarbon group and the hydrocarbon group-substituted silyl group decreased in the infrared absorption spectrum, and the peak intensity derived from the acid anhydride group decreased. Increasing, polymer dispersants.

(In the general formula (I) and the general formula (I'), L ¹ is a direct bond or a divalent linking group, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group, and-[CH ( R ³ ) -CH (R ⁴ ) -O] _x1- R ⁵ or-[(CH ₂ ) _y1- O] _z1- R ^{5 The} monovalent groups, R ³ and R ⁴ , are independent of each other. Hydrogen atom or methyl group, R ⁵ is hydrogen atom, hydrocarbon group, -CHO, -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ⁶ It is a monovalent group represented by, R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon group may have a substituent. X1 is an integer of 1 or more and 18 or less. , Y1 represents an integer of 1 or more and 5 or less, and z1 represents an integer of 1 or more and 18 or less.
In the general formula (I'), X ⁺ represents an organic cation. )

(In the general formula (II), R ⁷ represents a hydrogen atom or a methyl group, R ^P represents a monovalent protective group represented by the following general formula (A).
In the general formula (III), R ⁸ represents a hydrogen atom or a methyl group, L ² represents a direct bond or a divalent linking group, and Polymer represents a polymer chain having a structural unit represented by the following general formula (IV). show. )

(In the general formula ^{(A), R P1} represents a carbon atom or a silicon ^atom, R ^{P2, R P3} and ^{R P4} each independently represent a hydrogen atom or a hydrocarbon ^{group, R P5} is a hydrocarbon group or represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)

(In the general formula (IV), R ⁹ is a hydrogen atom or a methyl group, R P ^'is the following general formula (A' .n representing a monovalent protecting group represented by) 5 to 200 integer Represents.)

(In the general formula (A '), ^{R P'1} represents a carbon atom or a silicon atom, ^{R P'2, R P'3} and ^{R P'4} each independently represent a hydrogen atom or a hydrocarbon group , ^{R P'5} represents a hydrocarbon group or -OR ^{P'6, R P'6} is .R ^P'4 and ^{R P'5} represents a hydrocarbon group bonded to form a ring system with one another May be good.) The copolymer further comprises a hydrocarbon group, which may contain an —O— bond, in the side chain, which is derived from a monomer having a glass transition temperature value (Tgi) of less than 50 ° C. in the homopolymer. having a structural unit containing a polymeric dispersing agent according to claim 1. The copolymer further, the value of the glass transition temperature of a homopolymer (Tgi) is derived from a monomer of the above 50 ° C., has a structural unit containing a side chain hydrocarbon group, in claim 2 The polymer dispersant described. It contains (A) a coloring material, (B) a dispersant, and (C) a solvent, and the (B) dispersant contains the polymer dispersant according to any one of claims 1 to 3. Color material dispersion liquid. The color material dispersion liquid according to claim 4 , wherein the color material (A) is a metal lake color material of a dye. A colored resin composition containing the coloring material dispersion according to claim 4 or 5 , (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. The colored resin composition according to claim 6 , wherein the polyfunctional monomer (E) contains a phosphorus atom-containing polyfunctional monomer. A color filter comprising a transparent substrate and a colored layer on the transparent substrate, wherein at least one of the colored layers is a cured product of the colored resin composition according to claim 6 or 7. A liquid crystal display device having the color filter according to claim 8 , a facing substrate, and a liquid crystal layer located between the color filter and the facing substrate. A light emitting display device having the color filter according to claim 8 and a light emitting body. The method for producing a polymer dispersant according to any one of claims 1 to 3.
A block having a structural unit represented by the following general formula (II) and a structural unit having one or more reactive groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group. A step of reacting an organic phosphonic acid with the reactive group of the polymer, or
A graft having a structural unit represented by the following general formula (III) and a structural unit having one or more reactive groups selected from the group consisting of a glycidyl group, an alicyclic epoxy group, an oxetane group, and a hydroxyl group. A method for producing a polymer dispersant, which comprises any of the steps of reacting an organic phosphonic acid with the reactive group of the polymer.

(In the general formula (II), R ⁷ represents a hydrogen atom or a methyl group, R ^P represents a monovalent protective group represented by the following general formula (A).
In the general formula (III), R ⁸ represents a hydrogen atom or a methyl group, L ² represents a direct bond or a divalent linking group, and Polymer represents a polymer chain having a structural unit represented by the following general formula (IV). show. )

(In the general formula ^{(A), R P1} represents a carbon atom or a silicon ^atom, R ^{P2, R P3} and ^{R P4} each independently represent a hydrogen atom or a hydrocarbon ^{group, R P5} is a hydrocarbon group or represents -OR ^{P6, R P6} is ^{.R P4} and ^{R P5} represents a hydrocarbon group may be bonded together to form a ring structure.)

(In the general formula (IV), R ⁹ is a hydrogen atom or a methyl group, R P ^'is the following general formula (A' .n representing a monovalent protecting group represented by) 5 to 200 integer Represents.)

(In the general formula (A '), ^{R P'1} represents a carbon atom or a silicon atom, ^{R P'2, R P'3} and ^{R P'4} each independently represent a hydrogen atom or a hydrocarbon group , ^{R P'5} represents a hydrocarbon group or -OR ^{P'6, R P'6} is .R ^P'4 and ^{R P'5} represents a hydrocarbon group bonded to form a ring system with one another May be good.)

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