JP2020098347A - Colorant dispersion liquid, photosensitive coloring resin composition for color filters, color filter, liquid crystal display device, and organic electroluminescent display device - Google Patents

Abstract

To provide a colorant dispersion liquid with which it is possible to produce a photosensitive coloring resin composition that excels in colorant dispersion stability, in which occurrence of development residues is suppressed, and which excels in development adhesion and solvent redissolubility.SOLUTION: There is provided a colorant dispersion liquid containing a colorant, a dispersant and a solvent. The dispersant is at least one kind of a block copolymer including a (meth)acrylamide structural unit having an amino group and a salt-type block copolymer in which at least a portion of a nitrogen region at an end of the block copolymer including the (meth)acrylamide structural unit having the amino group and a specific compound form a salt, an amine value of the dispersant being 35-110 mgKOH/g, and a glass transition temperature of the dispersant being 30°C or higher.SELECTED DRAWING: None

Description

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

In recent years, the demand for liquid crystal displays has increased along with the development of personal computers, especially the development of portable personal computers. The penetration rate of mobile displays (cell phones, smartphones, tablet PCs) is also increasing, and the liquid crystal display market is expanding more and more. In addition, recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-light emission has also attracted attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image in a liquid crystal display device, the light that has passed through the color filter is colored as it is into the color of each pixel forming the color filter, and the lights of those colors are combined to form a color image. In this case, as the light source, in addition to the conventional cold cathode fluorescent lamp, a white light emitting organic light emitting element or a white light emitting inorganic light emitting element may be used. Further, in the organic light emitting display device, a color filter is used for color adjustment and the like.
Under such circumstances, there is an increasing demand for color filters to have high brightness, high contrast, and improved color reproducibility.

Here, the color filter is generally formed on a transparent substrate and a transparent substrate, a colored layer consisting of a colored pattern of the three primary colors of red, green and blue, and a transparent substrate on the transparent substrate so as to partition each colored pattern. And the formed light shielding part.

Among the methods for forming pixels in the color filter, the pigment dispersion method, which has excellent properties on average from the viewpoint of spectral characteristics, durability, pattern shape and accuracy, is most widely adopted.
In a color filter having pixels formed by using a pigment dispersion method, miniaturization of a pigment is being studied in order to realize high brightness and high contrast. It is considered that by miniaturizing the pigment, scattering of light passing through the color filter due to pigment particles is reduced, and higher brightness and higher contrast are achieved.
However, since the finely divided pigment particles are easily aggregated, there is a problem that the dispersibility and dispersion stability are reduced.

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

Further, in Patent Document 2, a dispersion for the purpose of obtaining a colored layer having high heat resistance and improved heat resistance even when a laked coloring material of a triarylmethane dye, which has high brightness but lower heat resistance than a pigment, is used. In a liquid and a colored resin composition, a graft copolymer having a constitutional unit derived from a dialkylamino(meth)acrylamide and a constitutional unit derived from a macromonomer as one dispersant, which is derived from the dialkylamino(meth)acrylamide. A dispersant in which the tertiary amino group of the structural unit of (1) forms a salt with an acidic organic phosphorus compound is disclosed. In Patent Document 2, when a color material in which a triarylmethane dye is combined with a specific anion and a specific dispersant are used in combination, not only the dispersibility and dispersion stability of the color material are improved. Furthermore, it is described that the obtained colored layer is also excellent in heat resistance.

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

With regard to color filters in recent years, it is necessary to solve various problems in mass production of color filters with the technology for improving the dispersibility of color materials for realizing the demands for high brightness and high contrast. .. That is, in order to increase the concentration of the coloring material in the resin composition, it is necessary to inevitably increase the amount of the dispersant, which causes problems such as generation of development residues and delay of development time. Further, when the concentration of the coloring material is increased and the content of the dispersant is increased, the amount of the binder is relatively decreased, which causes a problem that the colored resin layer is easily separated from the base substrate during development. Therefore, it is required for the colored resin composition to have high development adhesion, but there is a problem that it does not reach a practical level. Further, in the manufacturing process of the color filter, it is required that the solid content of the once dried colored resin composition is excellent in the property of being redissolved in the solvent and the redissolvability in the solvent. For example, when the photosensitive colored resin composition adheres to the tip of the die lip when performing coating with a die coater, solidification occurs due to drying, but when the coating is restarted, the solidified matter dissolves in the photosensitive coloring resin composition. If it is not easy to do, the solidified material on the die lip is partly peeled off and easily adheres to the colored layer of the color filter, which causes foreign matter defects. In particular, when the concentration of the coloring material in the colored resin composition is increased, the solvent re-solubility is liable to be insufficient, and there has been a problem that the yield is lowered due to the generation of the foreign matter in the manufacturing process of the color filter.
However, even with the copolymers described in Patent Documents 1 and 2, in addition to color material dispersion stability, various problems in mass production of color filters, development residue generation, development adhesion, solvent re-use, It was difficult to solve all of the solubility, as shown in Comparative Examples described later.

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

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

(In the general formula (I), R ¹ and R ^1′ are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, —[CH(R ⁶ )—CH(R ⁷ ). A divalent group represented by -O] _x -CH(R ⁶ )-CH(R ⁷ )- or [(CH ₂ ) _y- O] _z -(CH ₂ ) _y- , R ² and R ³ are Each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, and R ² and R ³ may be bonded to each other to form a ring structure, and R ⁶ and R ⁷ are each independently. It is a hydrogen atom or a methyl group, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.
In the general formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or —OR It represents ^e, R ^e is a straight chain of 1 to 20 carbon atoms, branched chain or cyclic alkyl group, a vinyl group, an optionally substituted phenyl group or a benzyl group, or an alkylene having 1 to 4 carbon atoms Represents a (meth)acryloyl group through a group. In the general formula (2), R ^b , R ^b′ , and R ^b″ each independently represent a hydrogen atom, an acidic group or its ester group, a straight chain having 1 to 20 carbon atoms which may have a substituent, It represents a branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -O- ^Rf , and ^Rf has a substituent. May be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a carbon number of 1 Represents a (meth)acryloyl group via an alkylene group of 4 to 4, X represents a chlorine atom, a bromine atom, or an iodine atom, In formula (3), R ^c and R ^d are each independently a hydrogen atom. Represents a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or —O—R ^e , and R ^e represents A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a (meth)acryloyl group having an alkylene group having 1 to 4 carbon atoms. Represents a group, provided that at least one of R ^c and R ^d contains a carbon atom.)

The photosensitive colored resin composition for a color filter according to the present invention is characterized by containing the coloring material dispersion liquid according to the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. ..

A color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a photosensitive material for a color filter according to the present invention. It is a colored layer formed by curing a colored resin composition.

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

According to the present invention, a coloring material dispersion liquid, which has excellent coloring material dispersion stability and is capable of producing a photosensitive colored resin composition having excellent development adhesion and solvent resolubility while suppressing the development residue, Excellent material dispersion stability, while suppressing development residue development, development adhesion, excellent solvent resolubility, also a photosensitive colored resin composition for a color filter capable of forming a colored layer excellent in contrast, It is possible to provide a color filter formed using the photosensitive colored resin composition for a color filter, and a liquid crystal display device and an organic light emitting display device having excellent display characteristics by using the color filter.

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

Hereinafter, the color material dispersion liquid, the photosensitive colored resin composition for a color filter, the color filter, the liquid crystal display device, and the organic light emitting display device according to the present invention will be sequentially described in detail.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and radiation, and the 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.
In the present invention, (meth)acrylic means each of acrylic and methacrylic, and (meth)acrylate means each of acrylate and methacrylate.

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

(In the general formula (I), R ¹ and R ^1′ are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, —[CH(R ⁶ )—CH(R ⁷ ). A divalent group represented by -O] _x -CH(R ⁶ )-CH(R ⁷ )- or [(CH ₂ ) _y- O] _z -(CH ₂ ) _y- , R ² and R ³ are Each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, and R ² and R ³ may be bonded to each other to form a ring structure, and R ⁶ and R ⁷ are each independently. It is a hydrogen atom or a methyl group, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.
In the general formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or —OR It represents ^e, R ^e is a straight chain of 1 to 20 carbon atoms, branched chain or cyclic alkyl group, a vinyl group, an optionally substituted phenyl group or a benzyl group, or an alkylene having 1 to 4 carbon atoms Represents a (meth)acryloyl group through a group. In the general formula (2), R ^b , R ^b′ , and R ^b″ each independently represent a hydrogen atom, an acidic group or its ester group, a straight chain having 1 to 20 carbon atoms which may have a substituent, It represents a branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -O- ^Rf , and ^Rf has a substituent. May be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a carbon number of 1 Represents a (meth)acryloyl group via an alkylene group of 4 to 4, X represents a chlorine atom, a bromine atom, or an iodine atom, In formula (3), R ^c and R ^d are each independently a hydrogen atom. Represents a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or —O—R ^e , and R ^e represents A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a (meth)acryloyl group having an alkylene group having 1 to 4 carbon atoms. Represents a group, provided that at least one of R ^c and R ^d contains a carbon atom.)

As a result of diligent studies, the present inventors have found that when the amine value of a specific block copolymer is low, the color material dispersion stability and the contrast of the colored layer do not reach a practical level, and when the amine value is too high, the solvent resolubility is high. However, it has been found that when the amine value is a specific value, the dispersion stability of the coloring material and the contrast of the colored layer are good, and the resolubility in the solvent is good.
The coloring material dispersion liquid of the present invention comprises, as a dispersant, a block copolymer (P1) having the specific amine value and the specific glass transition temperature and containing the structural unit represented by the general formula (I), and Since at least one salt-type block copolymer (P2) in which the block copolymer and the specific compound form a salt is used, the coloring material dispersibility and the coloring material dispersion stability are excellent. Even when the content of the dispersant in the color material is smaller than that of the conventional dispersant, it has excellent color material dispersibility and color material dispersion stability. It was also found that the use of pigments, which have been difficult to disperse in the past, not only enhances the dispersibility and dispersion stability but also has the effect of improving the brightness and the heat resistance. Further, when the pigment agglomerates are likely to precipitate when subjected to a heating step at a high temperature after fine dispersion, when the specific dispersant is included, the effect of suppressing the precipitation of the pigment agglomerates is obtained. I also found out that there is.
The structural unit represented by the general formula (I) has a terminal nitrogen moiety (—NR ² R ³ ) corresponding to an amino group and further has an amide group, and thus has high basicity. .. Further, the block copolymer (P1) containing the structural unit represented by the general formula (I) has an amine value larger than a specific value, so that the highly basic site is sufficiently adsorbed on the coloring material. It is presumed that since it is present as a solid block portion, the adsorptivity to the color material and the ability to maintain it after adsorption are particularly enhanced, and the color material dispersibility and the color material dispersion stability are excellent. On the other hand, since it has an amine value smaller than a specific value, it is presumed that the polarity does not become too strong, the solvent redissolvability is not impaired, and the colorant dispersibility and the colorant dispersion stability are improved. It
The coloring material is finely divided through a dispersion process, and the dispersant is appropriately adsorbed on the exposed surface to be stabilized.
However, in the color material applied to the substrate, when a high temperature of about 230° C. is applied in the color filter manufacturing process, the adsorptivity of the dispersant adsorbed to the color material is weakened by the thermal motion and partially desorbed. It is estimated that As a result, the surface of the coloring material exposed by the dispersant being desorbed becomes an environment in which the crystallinity of the coloring material is easily changed (transition, growth, etc.).
On the other hand, the structural unit represented by the general formula (I) has a strong basicity, and therefore has a strong adsorptivity with respect to the coloring material and a strong ability to be maintained after the adsorption. Therefore, even when a high temperature of about 230° C. is applied in the color filter manufacturing process, the detachment from the coloring material is extremely small, and as a result, the stability of the coloring material surface is maintained, and the change in tint due to crystal transition or the like occurs. It is presumed that the decrease in brightness can be suppressed. Further, it is presumed that the precipitation of aggregates can be suppressed in the color material in which pigment aggregates are easily deposited.

Further, the coloring material dispersion liquid of the present invention can produce a photosensitive colored resin composition which is excellent in development adhesion and solvent re-dissolvability while suppressing the generation of development residues.
Conventionally, a block copolymer containing a constitutional unit represented by the general formula (I) has been known as a pigment dispersant (Patent Document 1), but as a result of examination by the present inventors, Patent Document 1 When the described copolymer was used as a pigment dispersant, the development adhesion did not reach a practical level. In the pigment dispersant described in Patent Document 1, as shown in Comparative Examples to be described later, the copolymer contains a constitutional unit derived from an alkoxypolyalkylene glycol (meth)acrylate containing a polyalkyleneoxy chain, and thus glass. It is presumed that the transition temperature is low. When the glass transition temperature of the copolymer as the pigment dispersant is lower than the developer temperature, it is presumed that the molecular movement of the dispersant increases during development, resulting in a decrease in development adhesion.

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

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

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

The structural unit represented by the general formula (I) has basicity and functions as an adsorption site for the coloring material. Further, at least a part of the terminal nitrogen moiety of the constitutional unit represented by the general formula (I) and one or more compounds selected from the group consisting of the general formulas (1) to (3) are salts. When the salt is formed, the salt forming portion functions as a stronger adsorption site for the coloring material. It is presumed that the constitutional unit represented by the general formula (I) has a high basicity because it particularly contains an amide bond, and the adsorption function for the coloring material is further enhanced.
In the block copolymer used as the dispersant of the present invention, a block containing a structural unit represented by the general formula (I) (hereinafter sometimes referred to as an A block) and a block having a further hydrophilic property are usually used. (Hereinafter sometimes referred to as B block) is included. In the block copolymer having such a configuration, the A block adsorbing the color material and the B block having the solvent affinity share the function, and function as a color material dispersant.

[Block copolymer]
{A block}
(Structural unit represented by general formula (I))
In formula (I), R ¹ and R ^1′ are each independently a hydrogen atom or a methyl group. R ¹ is preferably a methyl group from the viewpoint of compatibility with other components.
A is an alkylene group having 1 to 8 carbon _{^{atoms, - [CH (R 6)}} -CH (R 7) -O] x -CH (R 6) -CH (R 7) - or _{[(CH 2) y} - O] _z- (CH ₂ ) _y- is a divalent group.
The alkylene group having 1 to 8 carbon atoms in A may be linear or branched, and examples thereof include methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, and various groups. Examples include a xylene group and various octylene groups. R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1 to 18, preferably an integer of 1 to 4, and more preferably an integer of 1 to 2.
From the viewpoint of dispersibility, the above A is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably, A is a methylene group, an ethylene group, a propylene group or a butylene group.

Examples of the hydrocarbon group in the hydrocarbon group which may contain a hetero atom in R ² and R ³ include an alkyl group, an aralkyl group and an aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and the like, and the number of carbon atoms of the alkyl group is 1 to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
Examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group and the like. The aryl group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms. The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is replaced with a hetero atom. Examples of the hetero atom that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom.
Further, the hydrogen atom in the hydrocarbon group may be substituted with an alkyl group having 1 to 5 carbon atoms, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom.

That R ² and R ³ bond to each other to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. A hetero atom may be contained in the ring structure formed by R ² and R ³ . The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring. In the present invention, even if having these cyclic amine structure, it is encompassed by the designation amino group (-NR 2 ^{R 3).}

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

Examples of the constitutional unit represented by the general formula (I) include dialkylaminoalkyl(meth)acrylamides such as dimethylaminoethyl(meth)acrylamide and dimethylaminopropyl(meth)acrylamide, and alkyl group-substituted amino group-containing (meth) Examples include, but are not limited to, acrylamide. From the viewpoint of compatibility with other components, an alkyl group-substituted amino group-containing methacrylamide such as dialkylaminoalkylmethacrylamide is preferable.
The constitutional unit represented by the general formula (I) may be one type or may include two or more types of constitutional units.

In the A block containing the structural unit represented by the general formula (I), three or more structural units represented by the general formula (I) are preferably contained. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferably contained in 3 to 100, more preferably 3 to 50, and further preferably 3 to 30.

The A block may have a constitutional unit other than the constitutional unit represented by the general formula (I) within a range in which the object of the present invention is achieved, and the block A is the same as the constitutional unit represented by the general formula (I). Any polymerizable structural unit can be contained. For example, as the constitutional unit other than the constitutional unit represented by the general formula (I) which may be contained in the A block portion, for example, a general formula such as an alkyl group-substituted amino group-containing (meth)acrylate or 1-vinylimidazole A structural unit having a basic group other than the structural unit represented by (I) or a structural unit mentioned in the B block described later can be used. Specifically, for example, in the general formula (II) described later, Examples include the structural units represented.
The content ratio of the structural unit represented by general formula (I) in the A block in the block copolymer before salt formation is 50 to 100% by mass based on the total mass of all the structural units of the A block. Is preferred, 80 to 100% by mass is more preferred, and 100% by mass is most preferred. This is because as the proportion of the structural unit represented by the general formula (I) is higher, the adsorptivity to the coloring material is improved, and the dispersibility and dispersion stability of the block copolymer are improved. The content ratio of the above structural unit is calculated from the charged mass when synthesizing the A block having the structural unit represented by the general formula (I).

Further, the content ratio of the structural unit represented by the general formula (I) in the block copolymer before salt formation is such that the amine value of the block copolymer before salt formation falls within the above-mentioned specific amine value range. It is not particularly limited as long as it is appropriately set, but from the viewpoint of good dispersibility and dispersion stability, it is 5 to 60 mass% with respect to the total mass of all the structural units of the block copolymer before salt formation. Is preferable, and 10 to 50% by mass is more preferable. The content ratio of each structural unit in the block copolymer is calculated from the charged mass when synthesizing the block copolymer before salt formation.
The structural unit represented by the general formula (I) has only to have an affinity with the coloring material, may be composed of one type, or may include two or more types of structural units. Good.

{B block}
The B block is a block that does not include the structural unit represented by the general formula (I) and that functions as a solvent-philic site. As the B block, a monomer having an unsaturated double bond, which is copolymerizable with the monomer for deriving the structural unit represented by the general formula (I), is appropriately selected depending on the solvent so as to have a solvent-philic property. It is preferably selected and used. As a guide, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. in the solvent used in combination is 20 (g/100 g solvent) or more.

The B block contains a structural unit appropriately selected in accordance with the solvent used from the viewpoint of improving the hydrophilicity and improving the hydrophilicity.
Examples of the structural unit that constitutes the B block include a monomer having an unsaturated double bond that is copolymerizable with the monomer that derives the structural unit represented by the general formula (I). The structural unit represented by (II) is preferable.

(In the general formula (II), A′ is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, —[CH(R ⁶ )—CH(R ⁷ ) -O] _x -R ⁸ or a monovalent group represented by -[(CH ₂ ) _y -O] _z -R ^8. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom, a hydrocarbon group, —CHO, —CH ₂ CHO, or a monovalent group represented by —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or a C 1 to C 5 group. It is an alkyl group.
The hydrocarbon group may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

In the general formula (II), A′ is a direct bond or a divalent linking group. The direct bond means that A′ does not have an atom, that is, C (carbon atom) in the general formula (II) and R ⁵ are bonded to each other without interposing another atom.
Examples of the divalent linking group for A′ include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, and an ether group having 1 to 10 carbon atoms (—R′— OR"-:R' and R" are each independently an alkylene group) or a combination thereof.
Among them, from the viewpoint of dispersibility, A′ in the general formula (II) is preferably a direct bond, a —CONH— group, or a divalent linking group containing a —COO— group.

In the general formula (II), R ⁵ is a hydrocarbon group, -[CH(R ⁶ )-CH(R ⁷ )-O] _x -R ⁸ or -[(CH ₂ ) _y- O] _z -R ^8. Indicates.
The hydrocarbon group for R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2 Examples thereof include an ethylhexyl group, a 2-ethoxyethyl group, a cyclopentyl group, a cyclohexyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group and a propenyl group. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity of the obtained polymer, it is preferable that the terminal of the alkenyl group has a double bond.
Examples of the substituent of the aliphatic hydrocarbon such as an alkyl group and an alkenyl group include a nitro group and a halogen atom.

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

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

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

It is preferable that R ⁵ is selected so as to have excellent compatibility with a solvent described later. Specifically, for example, the solvent is generally used as a solvent for the colored resin composition for a color filter. When a glycol ether acetate-based, ether-based, ester-based solvent used is used, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group and the like are preferable.

Further, R ⁵ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, an isocyanate group, etc. within a range that does not impair the dispersion performance of the block copolymer. After the synthesis of the polymer, the substituent may be added by reacting with the compound having the substituent.

The number of constitutional units constituting the B block is not particularly limited, but is 10 to 300 from the viewpoint that the solvent-philic portion and the parent colorant portion effectively act and the dispersibility of the colorant is improved. The number is preferably 10 to 100, more preferably 10 to 70.

In the B block in the block copolymer, the content ratio of the structural unit represented by the general formula (II) is based on the total mass of all the structural units of the B block from the viewpoint of improving the solvent affinity and the dispersibility of the coloring material. On the other hand, it is preferably 50 to 100% by mass, and more preferably 70 to 100% by mass. The content ratio of the above structural unit is calculated from the charged mass when synthesizing the B block.

Further, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (II) is such that the entire constitution of the block copolymer before salt formation is improved from the viewpoint of improving dispersibility of the coloring material. It is preferably 40 to 95% by mass, and more preferably 50 to 90% by mass, based on the total mass of the units. The content ratio of the above structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.

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

In the present invention, it is preferable that the B block of the block copolymer contains a structural unit derived from a hydroxyl group-containing monomer from the viewpoint of improving development adhesion and developing speed. When a structural unit derived from a hydroxyl group-containing monomer is contained, it easily interacts with glass or a metal that is usually used as a substrate, so that the development adhesion is improved, and the affinity with an alkali developing solution is improved. It is considered that the developing speed is improved.
The hydroxyl group here means an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

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

Further, in the block copolymer (P1) before salt formation, the content ratio of the structural unit derived from the hydroxyl group-containing monomer with respect to the total mass of all the structural units of the block copolymer from the viewpoint of improving development adhesion. , 1 to 70 mass% is preferable, 2 to 60 mass% is more preferable, 3 to 50 mass% is still more preferable, and 4 to 40 mass% is particularly preferable. The content ratio of the above structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.

Further, in the present invention, it is preferable that the B block contains a structural unit derived from an aromatic group-containing monomer from the viewpoint of improving the resolubility in a solvent. When the constitutional unit derived from the aromatic group-containing monomer is contained, compatibility with the solvent and other components is likely to be improved, and thus it is considered that the solvent re-solubility is improved.
As the constitutional unit derived from the aromatic group-containing monomer, a monomer containing an unsaturated double bond and an aromatic group which is copolymerizable with the monomer for deriving the constitutional unit represented by the general formula (I) can be used. .. Examples of such a monomer include acrylates such as benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and phenoxyethyl (meth)acrylate, styrenes such as styrene, vinyl ethers such as phenyl vinyl ether. The kind is mentioned.
As described below, the glass transition temperature of the dispersant used in the present invention is a specific value or more, from the viewpoint of improving the development adhesion, among others, the value of the glass transition temperature of the homopolymer of each monomer (Tgi) is It is preferable to use an aromatic group-containing monomer whose temperature is 0° C. or higher, and more preferable to use an aromatic group-containing monomer whose temperature is 10° C. or higher.
Among them, one or more selected from the group consisting of benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and phenoxyethyl (meth)acrylate from the viewpoint of easily improving resolubility. More preferably, it is one or more selected from the group consisting of benzyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

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

Further, among them, the B block having a solvent-philic property is composed of (i) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer, and (ii) a structural unit derived from a hydroxyl group and an aromatic group-containing monomer. It is preferable to contain at least one kind from the viewpoint of improving the development adhesiveness and the solvent redissolvability.

(I) In the case of containing a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer, respectively, with respect to 1 part by mass of the structural unit derived from an aromatic group-containing monomer, a structural unit derived from a hydroxyl group-containing monomer. Is preferably contained in an amount of 0.15 parts by mass or more, more preferably 0.5 parts by mass or more. This is because when it is at least the above lower limit, the development adhesion can be made excellent. Similarly, with respect to 1 part by mass of the structural unit of the aromatic group-containing monomer, the structural unit derived from the hydroxyl group-containing monomer is preferably contained in an amount of 15 parts by mass or less, and more preferably 7 parts by mass or less. It is because when it is at most the above upper limit, the solvent re-solubility can be made excellent. Among them, the value (Tgi) of the glass transition temperature of the homopolymer is 10 with respect to 1 part by mass of the structural unit derived from the aromatic group-containing monomer having the value (Tgi) of the glass transition temperature of the homopolymer of 10° C. or higher. It is particularly preferable to contain a structural unit derived from a hydroxyl group-containing monomer having a temperature of not less than 0° C. within the above range. When the content is not less than the above lower limit, the development adhesion can be further improved, and when the content is not more than the above upper limit, the solvent resolubility can be further improved.

Further, (ii) the hydroxyl group- and aromatic group-containing monomer in the structural unit derived from the hydroxyl group- and aromatic group-containing monomer, for example, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-acryloyloxyethyl- 2-hydroxyethyl-phthalic acid and the like can be mentioned. 2-Hydroxy-3-phenoxypropyl (meth)acrylate has a glass transition temperature value (Tgi) of a homopolymer of 10° C. or higher, and an effect obtained from a structural unit derived from a hydroxyl group-containing monomer and an aromatic group. It is preferably used from the viewpoint that any of the effects obtained from the structural unit derived from the group-containing monomer can be obtained. That is, it is preferable in that the development adhesion, the development speed, and the solvent re-solubility are improved.
(Ii) When a constitutional unit derived from a monomer containing a hydroxyl group and an aromatic group is contained, one constitutional unit can improve the development adhesion, the development rate, and the solvent re-solubility. There is also an advantage that the introduction ratio can be increased.

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

In the block copolymer (P1) before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer is appropriately set so that the acid value of the block copolymer falls within the specific acid value range. There is no particular limitation as long as it is carried out, but it is preferably 0.05 to 4.5% by mass, and 0.07 to 3.7% by mass based on the total mass of all the structural units of the block copolymer before salt formation. % Is more preferable.
The constitutional unit derived from the carboxy group-containing monomer may consist of one type, or may include two or more types of constitutional units.

Further, as will be described later, the glass transition temperature (Tgi) of the homopolymer of the monomer is 10 since the glass transition temperature of the dispersant used in the present invention is not less than a specific value and the development adhesion is improved. The total amount of the monomers having a temperature of not less than 0° C. in the B block is preferably 75% by mass or more, more preferably 85% by mass or more.

In the block copolymer (P1), the ratio m/n of the number m of units of the constitutional unit of the A block and the number n of units of the constitutional unit of the B block is within a range of 0.05 to 1.5. Is preferable, and the range of 0.1 to 1.0 is more preferable from the viewpoint of dispersibility and dispersion stability of the coloring material.

In addition, the amine value of the block copolymer (P1) before salt formation is 35 mgKOH/g or more as a lower limit from the viewpoint of colorant dispersibility and dispersion stability. Among them, the amine value of the block copolymer before salt formation is more preferably 40 mgKOH/g or more, and even more preferably 50 mgKOH/g or more, from the viewpoint of more excellent dispersion stability. In addition, the amine value of the block copolymer before salt formation is 110 mgKOH/g or less as an upper limit from the viewpoint of solvent re-solubility. Among them, the amine value of the block copolymer before salt formation is more preferably 95 mgKOH/g or less, and 80 mgKOH/g or less, from the viewpoint of excellent compatibility with other components and good solvent re-solubility. Is even more preferable.
In the present invention, the amine value of the block copolymer (P1) before salt formation is equivalent to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the block copolymer before salt formation. It represents the mass (mg) of potassium hydroxide and is a value measured by the method described in JIS K7237.

The block copolymer (P1) before salt formation has a carboxy group, and the acid value of the block copolymer is preferably 18 mgKOH/g or less, more preferably 16 mgKOH/g or less. .. This is because it is possible to prevent deterioration of solvent resolubility and development adhesion.
In addition, the block copolymer (P1) before salt formation has a carboxy group, and the acid value of the block copolymer (P1) is preferably 1 mgKOH/g or more, and preferably 2 mgKOH/g or more. It is more preferable that there is. This is because the effect of suppressing the development residue is improved.
In the present invention, the acid value of the block copolymer (P1) before salt formation is the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the block copolymer. And is a value measured by the method described in JIS K 0070.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, and preferably 2000 to 15000, from the viewpoint of making the colorant dispersibility and dispersion stability favorable. More preferably, and still more preferably 3000 to 12000.
Here, the weight average molecular weight (Mw) is obtained as a standard polystyrene conversion value by gel permeation chromatography (GPC).
In the present invention, the weight average molecular weight Mw of the block copolymer is determined as a standard polystyrene conversion value by GPC (gel permeation chromatography). The measurement was carried out by using HLC-8120GPC manufactured by Tosoh Corporation, the eluting solvent was N-methylpyrrolidone to which 0.01 mol/liter of lithium bromide was added, and polystyrene standards for calibration curves were Mw377400, 210500, 96000, 50400. , 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories, Inc.) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M x 2 measuring columns (Tosoh). (Manufactured by Co., Ltd.). The macromonomer, the salt-type block copolymer, and the graft copolymer, which are raw materials of the block copolymer, are also subjected to the above conditions.

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

The method for producing the block copolymer is not particularly limited. Although the block copolymer can be produced by a known method, it is preferably produced by the living polymerization method. This is because chain transfer and deactivation hardly occur, a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include a living radical polymerization method, a living anionic polymerization method such as a group transfer polymerization method, and a living cationic polymerization method. A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, the block copolymer can be produced by first producing the A block and then polymerizing the constituent units constituting the B block into the A block. In the above production method, the order of polymerization of the A block and the B block can be reversed. It is also possible to manufacture the A block and the B block separately and then couple the A block and the B block.

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

(One or more compounds selected from the group consisting of the general formulas (1) to (3))
In the general formulas (1) to (3), R ^a , R ^b , R ^b′ , R ^b″ , R ^c , R ^d , R ^e , and R ^{f have} a straight chain or branched chain having 1 to 20 carbon atoms. Alternatively, the cyclic alkyl group may be linear or branched, and may include a cyclic structure. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- Examples thereof include an undecyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a tetradecyl group, an octadecyl group, etc. Preferably, a straight chain, branched chain or cyclic alkyl group having 1 to 15 carbon atoms is mentioned, and more preferably carbon number. 1 to 8 linear, branched or cyclic alkyl groups can be mentioned.
Further, in R ^a , R ^c , R ^d , and R ^e , examples of the substituent of the phenyl group or the benzyl group which may have a substituent include, for example, an alkyl group having 1 to 5 carbon atoms, and an acyl group. , An acyloxy group and the like.

In R ^b , R ^b′ , R ^b″ , and R ^f , the substituent of the phenyl group or the benzyl group, which may have a substituent, is, for example, an acidic group or an ester group thereof, or a carbon atom having 1 to 1 carbon atoms. The alkyl group, the acyl group, the acyloxy group and the like of 5 are mentioned.
Further, in R ^b , R ^b′ , R ^b″ , and R ^f , as a substituent of a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, which may have a substituent, or a vinyl group. Include an acidic group or its ester group, a phenyl group, an acyl group, an acyloxy group and the like.
The acidic group in R ^b , R ^b′ , R ^b″ , and R ^f refers to a group that exhibits acidity by releasing a proton in water. Specific examples of the acidic group include a carboxy group (—COOH), sulfo group _(-SO 3 H), a phosphono group (-P (= O) (OH ) 2), phosphinico group (> P (= O) ( OH)), boronic acid group (-B _(OH) 2), Examples thereof include a borinic acid group (>BOH) and the like, which may be an anion in which a hydrogen atom is dissociated such as a carboxylato group (—COO ⁻ ), and a salt with an alkali metal ion such as sodium ion or potassium ion. It may be the acid salt formed.
As the ester group of the acidic group, a carboxylic acid ester (-COOR), sulfonate _(-SO 3 R), phosphoric acid ester _{(-P (= O) (OR} ) 2), (> P (= O )(OR)), boronic acid ester (—B(OR) ₂ ), borinic acid ester (>BOR) and the like. Among them, the ester group of the acidic group is preferably a carboxylic acid ester (-COOR) from the viewpoint of dispersibility and dispersion stability. R is a hydrocarbon group and is not particularly limited, but from the viewpoint of dispersibility and dispersion stability, it is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group or an ethyl group. More preferable.

From the viewpoint of dispersibility, dispersion stability, alkali developability, and development residue suppression, the compound of the general formula (2) is a carboxy group, a boronic acid group, a boric acid group, their anions, and alkali metal salts thereof. , And one or more functional groups selected from these ester groups are preferable, and among them, it is more preferable to have a functional group selected from a carboxy group, a carboxylato group, a carboxylate group, and a carboxylate ester. It is particularly preferable to contain a carboxy group.
When the compound of the general formula (2) has an acidic group and an ester group thereof (hereinafter referred to as an acidic group, etc.), both of the acidic group side of the compound and the halogen atom side hydrocarbon have terminal nitrogen. Although it is possible to form a salt with the site, it is presumed that the terminal nitrogen site and the hydrocarbon on the halogen atom side stably form a salt, as compared with the case where the terminal nitrogen site and the acidic group form a salt. It is presumed that the coloring material is adsorbed on the stable salt-forming site to improve the dispersibility and the dispersion stability. Further, when the compound of the general formula (2) has an acidic group or the like, the dispersant has excellent alkali developability. In particular, when the block copolymer (P1) has an acid value, that is, the solvent-philic portion (B block) of the block copolymer (P1) contains a structural unit derived from an acidic group-containing monomer such as a carboxy group. In the case where the acid group has an acid value, the acidic group or the like which increases the acid value at the salt forming site has a high effect of suppressing the development residue. It should be noted that having an acidic group or the like that increases the acid value at the salt forming site means that the acidic group forming a salt by reacting with the terminal nitrogen site of the structural unit represented by the general formula (I). It means that it has an acidic group that does not form a salt directly with the nitrogen moiety. For example, when the compound of the general formula (2) has an acidic group or the like, the compound of the general formula (2) has a terminal nitrogen moiety and a halogen atom side carbonization which the structural unit represented by the general formula (I) has. Since hydrogen forms a salt, the salt forming site has an acid group or the like that does not form a salt, thereby increasing the acid value.

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

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

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

Examples of the compound represented by the general formula (1) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid and mono-n-propylsulfuric acid. A hydrate such as p-toluenesulfonic acid monohydrate may be used. Examples of the compound represented by the general formula (2) include methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, Tetradecyl chloride, hexadecyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethyl Benzoic acid, 4-iodophenyl benzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3-(bromomethyl)phenylboronic acid and the like can be mentioned. Examples of the compound represented by the general formula (3) include monobutylphosphoric acid, dibutylphosphoric acid, methylphosphoric acid, dibenzylphosphoric acid, diphenylphosphoric acid, phenylphosphinic acid, phenylphosphonic acid, and dimethacryloyloxyethyl acid phosphate. ..
From the viewpoint of particularly excellent dispersion stability, a group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, dibutylphosphoric acid, benzyl chloride, benzyl bromide, vinylsulfonic acid, and p-toluenesulfonic acid monohydrate. At least one selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl bromide, vinylsulfonic acid, and p-toluenesulfonic acid monohydrate is preferably used. Is preferred.
In addition, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodo, from the viewpoint that the effect of suppressing development residues is improved by combination with the block copolymer (P1) having excellent dispersion stability and an acid value. One or more selected from the group consisting of phenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid are also preferably used.

In the salt-type block copolymer, the content of at least one compound selected from the group consisting of the general formulas (1) to (3) is such that the content of the terminal of the structural unit represented by the general formula (I) is Since it forms a salt with a nitrogen site, the group consisting of the above general formulas (1) to (3) per 1 mol of the terminal nitrogen site of the structural unit represented by the general formula (I). The amount of one or more compounds selected from is preferably 0.01 mol or more, more preferably 0.1 mol or more, further preferably 0.2 mol or more, and 0.3 mol or more. Is particularly preferable. When it is at least the above lower limit, the effect of improving dispersibility of the coloring material due to salt formation is likely to be obtained. Similarly, the amount is preferably 1 mol or less, more preferably 0.8 mol or less, further preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When it is at most the above upper limit, the development adhesion and the solvent re-dissolvability can be made excellent.
The one or more compounds selected from the group consisting of the general formulas (1) to (3) may be used alone or in combination of two or more. When two or more kinds are combined, the total content is preferably within the above range.

As a method for preparing the salt-type block copolymer, one or more compounds selected from the group consisting of the general formulas (1) to (3) are added to a solvent in which the block copolymer is dissolved or dispersed. However, a method of stirring, and if necessary, heating may be mentioned.
The terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer, and one or more compounds selected from the group consisting of the general formulas (1) to (3). The formation of a salt and the ratio thereof can be confirmed by a known method such as NMR.

The amine value of the obtained salt-type block copolymer is smaller than that of the block copolymer before salt formation by the amount of salt formation. However, since the salt-forming site becomes a coloring material adsorption site that is similar to or rather reinforced with the terminal nitrogen site corresponding to the amino group, there is a tendency for the coloring material dispersibility and the coloring material dispersion stability to improve due to salt formation. is there. Further, like the amino group, the salt-forming site adversely affects the solvent re-solubility when it is too much. Therefore, in the present invention, the amine value of the block copolymer (P1) before salt formation can be used as an index for improving the color material dispersion stability and the solvent re-solubility.
The amine value of the obtained salt-type block copolymer is preferably 0 to 110 mgKOH/g, and more preferably 0 to 100 mgKOH/g or less.
When it is at most the above upper limit, the compatibility with other components will be excellent and the solvent re-solubility will be good.

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

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

In the salt type block copolymer (P2), when the acid value of the block copolymer (P1) before salt formation is 0 mgKOH/g, the salt type block copolymer (P2) has an acid value. However, the effect of suppressing the development residue is hardly improved. On the other hand, when the acid value of the block copolymer (P1) before salt formation is 1 mgKOH/g or more, the acid value of the salt-type block copolymer (P2) is the acid value of the block copolymer (P1). When the value is larger than the value, the effect of suppressing the development residue is improved.
The acid value of the block copolymer (P1) is due to a structural unit derived from an acidic group-containing monomer such as a carboxy group present in the B block which is a hydrophilic portion, and the acidic group has a hydrophilic portion. Since it is located very close to other components (alkali-soluble resin, polyfunctional monomer, etc.) other than the coloring material and the developing solution, it is thought that the development residue and solvent re-solubility are greatly affected. .. On the other hand, the increased acid value of the salt-type block copolymer (P2) is due to the acidic group bonded to the adsorption site of the coloring material, so the acidic group is separated from the other components. Therefore, it is considered that the influence on the development residue and solvent resolubility is small.
Further, when the acid value of the block copolymer (P1) before salt formation is 1 mgKOH/g or more, the acid value of the salt-type block copolymer (P2) after salt formation is the block copolymer (P1). When the value is larger than the acid value of, the dispersant as a whole has a wide acid value because the solvent-philic site and the coloring material adsorption site have acidic groups. Under conditions where the solvent-philic part has developability, the coloring material is easily adsorbed by the dispersant that dissolves, and the coloring material is not left behind on the base material, thus suppressing the generation of residues. Is estimated to improve.

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

Acid value of salt-type block copolymer (P2)={total acid value of the compound represented by the general formula (1) or (3) used for salt formation-acid value consumed by salt formation}+salt Acid value of pre-formation block copolymer (P1) Here, the total acid value of the compound represented by the general formula (1) or (3) used for the salt formation is as described in JIS K 0070. It can be measured by a method. On the other hand, the acid value consumed by salt formation is calculated from the salt formation ratio obtained by NMR.
The acid value consumed by the salt formation is, for example, by measuring a 13 C-NMR spectrum using a nuclear magnetic resonance apparatus, and in the obtained spectrum data, nitrogen which is not salt-formed at the terminal nitrogen site. Calculate the ratio of the number of terminal nitrogen sites in the salt formation to the total number of terminal nitrogen sites from the ratio of the integrated value of the carbon atom peaks adjacent to the atom and the carbon atom peaks adjacent to the nitrogen atom in the salt formation. .. (Amine value of pre-salt-forming block copolymer (P1) measured by the method described in JIS K 7237)×(Salt-forming terminal nitrogen site ratio (%)/calculated from 13 C-NMR spectrum)/ 100), the consumed amine value is calculated, and this value becomes the same as the acid value consumed by salt formation.
However, when 1 mol or less of the compound represented by the general formula (1) forms a salt with 1 mol of the terminal nitrogen moiety of the constitutional unit represented by the general formula (I), an acidic group is 1 In the case of forming a salt of the compound represented by the general formula (3) in an amount of 1 mol or less, or in the form of a salt of the compound represented by the general formula (3) having two acidic groups in an amount of 0.5 mol or less. In the case of forming the salt, if the total amount of the acidic group forms a salt with the terminal nitrogen moiety of the structural unit represented by the general formula (I), the acidic group in the salt-type block copolymer after the salt is formed. Has no acid value and therefore has the same acid value as the block copolymer before salt formation.
On the other hand, when the compound represented by the general formula (3) having two acidic groups is added in a mole number higher than the above, there is an acidic group which does not form a salt in the dispersant even after the salt formation. Therefore, as in the above formula, the acid value of the non-salt-forming acidic group is added to the acid value of the block copolymer before salt formation to calculate the acid value of the dispersant.

Further, in the present invention, the glass transition temperature of the dispersant is 30° C. or higher. That is, regardless of whether the dispersant is the block copolymer (P1) or the salt-type block copolymer (P2), the glass transition temperature thereof is 30° C. or higher.
When the glass transition temperature of the dispersant is lower than 30° C., particularly when the temperature is equal to or lower than the temperature of the developing solution (usually about 23° C.), the development adhesion is lowered. This is presumed to be because when the glass transition temperature is equal to or lower than the temperature of the developing solution, the movement of the dispersant during development becomes large, and as a result, the development adhesion is deteriorated.
The glass transition temperature of the dispersant is preferably 45° C. or higher, and more preferably 60° C. or higher, from the viewpoint of enhancing the development adhesion and the effect of suppressing the change of the coloring material such as the precipitation of aggregates. On the other hand, it is preferably 200° C. or lower from the viewpoint of operability during use such as easy precise weighing.
The glass transition temperature of the dispersant in the present invention is determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

However, the glass transition temperature (Tg) of the block copolymer without salt formation can be calculated by the following formula and used as an index.
1/Tg=Σ(Xi/Tgi)
Here, it is assumed that the block copolymer is a copolymer of n monomer components from i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum of i=1 to n. The value of the glass transition temperature (Tgi) of the homopolymer of each monomer may be the value given in Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).
The glass transition temperature based on the calculated value is almost the same as the value measured by the DSC, as will be described later in Examples, and can be used as an index of the glass transition temperature of the block copolymer without salt formation. it can.

In the color material dispersion liquid of the present invention, at least one of the block copolymer and the salt-type block copolymer is used as the dispersant, and the content thereof is the kind of the color material to be used, and further for the color filter described later. It is appropriately selected according to the solid content concentration in the photosensitive colored resin composition.
From the viewpoint of dispersibility and dispersion stability, the content of the dispersant is 3 to 45 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion liquid. It is preferable to mix them.
In particular, when forming a coating film or a coloring layer having a high coloring material concentration, the content of the dispersant is 3 to 25 parts by mass, more preferably 100 parts by mass of the total solid content in the coloring material dispersion liquid. It is preferable to add 5 to 20 parts by mass.
In addition, in the present invention, the solid content is all other than the above-mentioned solvent, and also includes a monomer dissolved in the solvent.

<Color material>
In the present invention, the coloring material is not particularly limited as long as it can produce a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments and dispersible dyes may be used alone. Or two or more kinds can be mixed and used. Among them, organic pigments are preferably used because they have high color developability and high heat resistance. As the organic pigment, for example, a compound classified into Pigment in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) The numbered ones can be mentioned.

C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175;
C. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57: 1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60;
C. I. Pigment Green 7, 36, 58;
C. I. Pigment Brown 23, 25;
C. I. Pigment Black 1, 7.

Further, specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, dark blue, and oxidation. Examples include chrome green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

For example, when forming a pattern of a light-shielding layer as a color filter photosensitive colored resin composition for a color filter dispersion liquid of the present invention on a substrate of a color filter, a black pigment having a high light-shielding property is used in the ink. Compound. As the black pigment having a high light-shielding property, for example, an inorganic pigment such as carbon black or ferrosoferric oxide, or an organic pigment such as cyanine black can be used.

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

In the present invention, the coloring material preferably contains at least one selected from the group consisting of phthalocyanine pigments, diketopyrrolopyrrole pigments, and quinophthalone pigments.
When the coloring material contains a phthalocyanine-based pigment, it is preferable because it interacts with the specific dispersant to improve brightness and heat resistance. When the coloring material contains at least one selected from the group consisting of a diketopyrrolopyrrole pigment and a quinophthalone pigment, in which the pigment aggregates are likely to be precipitated by a high temperature heating step after fine dispersion. It is preferable that the pigment aggregates are prevented from precipitating even if they interact with the specific dispersant and undergo a high temperature heating step after fine dispersion.
With a normal dispersant, the coloring material is easily desorbed by heating and the coloring material surface is exposed, so that the coloring material is likely to change. However, the specific dispersing agent used in the present invention has a strong adsorption force to the coloring material. Therefore, the dispersant is less desorbed during heating. Therefore, the crystallinity is likely to change by heating, such as phthalocyanine pigments, or the pigment is liable to decrease in brightness due to color change, and pigment aggregates are deposited such as diketopyrrolopyrrole pigments and quinophthalone pigments. Even if the pigment is easy, the above-mentioned changes can be suppressed by maintaining the adsorption of the dispersant during heating.

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

The average dispersed particle diameter of the color material in the color material dispersion liquid varies depending on the type of the color material used, but is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. preferable.
The average dispersed particle diameter of the coloring material in the coloring material dispersion liquid is the dispersed particle diameter of the coloring material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. Is. The particle size can be measured by a laser light scattering particle size distribution meter by appropriately diluting the color material dispersion liquid with a solvent used for the color material dispersion liquid to a concentration that can be measured by the laser light scattering particle size distribution meter (for example, 1000 times). And the like) and a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.) can be used to measure at 23° C. by a dynamic light scattering method. The average distribution particle size here is a volume average particle size.

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

In the color material dispersion liquid of the present invention, the content of the color material is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of the coloring material is 5 to 80 parts by mass, more preferably 8 to 70 parts by mass, based on 100 parts by mass of the total solid content in the coloring material dispersion liquid. It is preferable to mix them.
Particularly when forming a coating film or a coloring layer having a high coloring material concentration, the proportion of 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, relative to 100 parts by mass of the total solid content in the coloring material dispersion liquid. It is preferable to blend in.

[solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the color material dispersion liquid and can dissolve or disperse these components. The solvent may be used alone or in combination of two or more kinds.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester-based solvents such as ethyl lactate and cyclohexanol acetate; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1 -Glycol ether acetate-based solvents such as butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate; carbitol acetate-based solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); propylene glycol diacetate Diacetates such as 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol Glycol ether solvent such as dimethyl ether; aprotic amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; lactone solvent such as γ-butyrolactone; cyclic ether solvent such as tetrahydrofuran Unsaturated solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene Are listed. Among these solvents, glycol ether acetate-based solvent, carbitol acetate-based solvent, glycol ether-based solvent, and ester-based solvent are preferably used from the viewpoint of solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, Also, it is preferable that it is at least one selected from the group consisting of 3-methoxybutyl acetate from the viewpoint of solubility of other components and coating suitability.

The color material dispersion liquid of the present invention preferably contains the solvent as described above in a range of usually 55 to 95 mass% with respect to the total amount of the color material dispersion liquid containing the solvent. %, and more preferably 70 to 88% by mass. If the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. Further, if the amount of the solvent is too large, the concentration of the coloring material decreases, and it may be difficult to achieve the target chromaticity coordinates.

(Other ingredients)
The color material dispersion liquid of the present invention may further contain a dispersion auxiliary resin and other components, if necessary, as long as the effects of the present invention are not impaired.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the photosensitive colored resin composition for color filters described below. The steric hindrance of the alkali-soluble resin makes it difficult for the coloring material particles to come into contact with each other, which may stabilize the dispersion and may have an effect of reducing the dispersant due to the dispersion stabilizing effect.
Further, other components include, for example, a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, an anti-cissing agent, an antioxidant, an anti-agglomeration agent, an ultraviolet absorber. And so on.

The color material dispersion liquid of the present invention is used as a preliminary preparation for preparing a photosensitive colored resin composition for a color filter described later. That is, the color material dispersion liquid is preliminarily prepared in a step before preparing a photosensitive color resin composition for a color filter described later, (mass of color material component in composition)/(color material component in composition) It is a coloring material dispersion liquid having a high solid content mass ratio other than. Specifically, the ratio (mass of coloring material component in composition)/(mass of solid content other than coloring material component in composition) ratio is usually 1.0 or more. By mixing the color material dispersion liquid with each of the components described below, it is possible to prepare a photosensitive color resin composition for a color filter having excellent dispersibility.

[Method for producing color material dispersion]
In the present invention, the method for producing a colorant dispersion is a method in which the colorant is a colorant dispersion dispersed in a solvent by a dispersant for the block copolymer or the salt-type block copolymer. There is no particular limitation as long as it exists. Above all, it is preferable to use one of the following two production methods from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

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

A second method for producing a colorant dispersion according to the present invention when a dispersant that is a salt-type block copolymer is used is a solvent, the block copolymer, and the general formulas (1) to ( 3) at least one compound selected from the group consisting of and a colorant are mixed, and at least a part of the terminal nitrogen moiety of the constitutional unit represented by the general formula (I), and the compound And a step of dispersing the coloring material while forming a salt.

In the case of using a salt-type block copolymer, according to the first production method, after preparing the salt-type block copolymer, the coloring material is dispersed by using the salt-type block copolymer as a dispersant. Therefore, it is possible to accurately confirm the reaction end point and the reaction rate of the block copolymer before the salt formation and the one or more compounds selected from the group consisting of the general formulas (1) to (3). preferable.
In addition, according to the second production method, since the coloring material is dispersed while preparing the dispersant for the salt-type block copolymer, the salt-type block copolymer does not self-aggregate and the coloring material is dispersed. The liquid can be efficiently prepared and the dispersibility can be improved.

In the first manufacturing method and the second manufacturing method, the coloring material can be dispersed using a conventionally known disperser.
Specific examples of the disperser include roll mills such as two rolls and three rolls, ball mills such as ball mills and vibration ball mills, paint conditioners, bead mills such as continuous disc type bead mills and continuous annular type bead mills. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 3.0 mm, more preferably 0.05 to 2.0 mm.

Specifically, it is possible to perform preliminary dispersion with 2.0 mm zirconia beads having a relatively large bead diameter, and further perform main dispersion with 0.1 mm zirconia beads having a relatively small bead diameter. After dispersion, it is preferable to filter with a filter of 0.5 to 2 μm.

[Photosensitive colored resin composition for color filter]
The photosensitive colored resin composition for a color filter according to the present invention is characterized by containing the coloring material dispersion liquid according to the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.
The photosensitive color resin composition for a color filter of the present invention, by using the color material dispersion liquid according to the present invention, is excellent in color material dispersion stability, while suppressing development residue development, development adhesion, solvent. It is possible to form a colored layer having excellent redissolvability and excellent contrast.

The photosensitive colored resin composition for a color filter of the present invention contains at least a coloring material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. Other components may be further contained as long as the effect is not impaired. Hereinafter, each component contained in the photosensitive colored resin composition for a color filter of the present invention will be described, but the dispersant, the coloring material, and the solvent are the same as those described in the coloring material dispersion liquid of the present invention. Therefore, the description thereof is omitted here.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and is appropriately selected from those which are soluble in a developer used in pattern formation, particularly preferably an alkali developer. Can be used.
The preferred alkali-soluble resin in the present invention is a resin having a carboxy group as an acidic group, and specific examples thereof include an acrylic copolymer having a carboxy group and an epoxy (meth)acrylate resin having a carboxy group. Particularly preferred among these are those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, two or more kinds of these acrylic copolymers and epoxy acrylate resins may be mixed and used.

The acrylic copolymer having a carboxy group is obtained by copolymerizing a carboxy group-containing ethylenically unsaturated monomer and another ethylenically unsaturated monomer.

Specific examples of the acrylic copolymer having a carboxy group include those described in JP 2013-029832 A, specifically, for example, methyl (meth)acrylate, ethyl (meth). ) A copolymer composed of a monomer having no carboxy group such as acrylate and one or more kinds selected from (meth)acrylic acid and its anhydride can be exemplified. Further, to the above copolymer, for example, a glycidyl group, a polymer having an ethylenically unsaturated bond introduced by, for example, adding an ethylenically unsaturated compound having a reactive functional group such as a hydroxyl group, and the like can be exemplified. It is not something that will be done.
Among these, the addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is particularly preferable in that the sensitivity and film strength of the colored layer will be more stable.

The copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer in the carboxy group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, if the copolymerization ratio of the carboxy group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film in an alkali developing solution is lowered and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by mass, the pattern tends to be chipped or the surface of the pattern becomes rough during development with an alkaline developer.

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

The epoxy (meth)acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth) obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones and used. The epoxy (meth)acrylate resin having a carboxy group may be used alone or in combination of two or more.

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

<Polyfunctional monomer>
The polyfunctional monomer used in the photosensitive colored resin composition for a color filter is not particularly limited as long as it can be polymerized by the photoinitiator described below, and usually has two or more ethylenically unsaturated double bonds. A compound having is used, and it is particularly preferably a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups.
Such a polyfunctional (meth)acrylate may be appropriately selected from conventionally known ones and used. Specific examples thereof include those described in JP 2013-029832 A.

These polyfunctional (meth)acrylates may be used alone or in combination of two or more. In addition, when the photosensitive color resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Those having the above are preferable, and poly(meth)acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products are preferable. Specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol trichloride (Meth)acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth) ) Succinic acid modified products of acrylate, dipentaerythritol hexa(meth)acrylate and the like are preferable.
The content of the polyfunctional monomer used in the photosensitive colored resin composition for a color filter is not particularly limited, but the polyfunctional monomer is preferably 5 relative to the total solid content of the photosensitive colored resin composition for a color filter. It is in the range of -60 mass%, more preferably 10-40 mass%. If the content of the polyfunctional monomer is less than the above lower limit value, the photo-curing does not proceed sufficiently and the exposed part may be eluted during the development. May decrease.

<Photoinitiator>
The photoinitiator used in the color filter photosensitive colored resin composition is not particularly limited, and one kind or a combination of two or more kinds can be used from among various conventionally known photoinitiators. Specific examples thereof include those described in JP 2013-029832 A.
As the photoinitiator, only one kind may be used, but two or more kinds of compounds may be used in combination. As the photoinitiator, it is preferable to include an oxime ester, among others, from the viewpoint that the effect of suppressing the occurrence of pattern defects and the effect of suppressing the generation of water stains are high. As the oxime ester, those having an aromatic ring are preferable, and those having a condensed ring containing an aromatic ring are preferable from the viewpoint of reducing the contamination of the photosensitive colored resin composition for a color filter and the contamination of the device due to decomposition products. It is more preferable to have a condensed ring containing a benzene ring and a hetero ring.
Examples of the oxime ester include 1,2-octadion-1-[4-(phenylthio)-, 2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H. -Carbazol-3-yl]-, 1-(o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, JP 2010-527339, JP 2010-527338, JP 2013-2013. It can be appropriately selected from the oxime ester-based photopolymerization initiators described in 041153 and the like. As a commercially available product, Irgacure OXE-01, Irgacure OXE-02 (above manufactured by BASF), ADEKA OPT-N-1919 (manufactured by Asahi Denka Co., Ltd.) and the like may be used.

Further, it is preferable to use the oxime ester in combination with a photoinitiator having a tertiary amine structure from the viewpoint of improving the sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure which is an oxygen quencher in the molecule, the radicals generated from the initiator are hard to be deactivated by oxygen and the sensitivity can be improved. is there. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF), 4,4′-bis(diethylamino)benzophenone (for example, High Cure ABP, Kawaguchi Yakuhin) and the like.

The content of the photoinitiator used in the photosensitive colored resin composition for a color filter is not particularly limited, but the photoinitiator is preferably 3 to the total solid content of the photosensitive colored resin composition for a color filter. It is in the range of 40% by mass, more preferably 10 to 30% by mass. If the content is less than the lower limit, the photo-curing does not proceed sufficiently, and the exposed portion may elute during development. On the other hand, if the content is more than the upper limit, the yellowing of the resulting colored layer becomes strong and the brightness is high. It may decrease.

<Optional additive components>
The photosensitive colored resin composition for color filters may contain various additives as required.
Examples of the additives include, in addition to antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, etc. Can be mentioned.

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

When an antioxidant is used, its amount is not particularly limited as long as it does not impair the effects of the present invention. The antioxidant is preferably added in an amount of 0.1 to 5.0% by mass, preferably 0.5 to 5.0% by mass, based on the total solid content in the photosensitive colored resin composition for a color filter. It is more preferably 4.0% by mass. When it is at least the above lower limit, the heat resistance is excellent. On the other hand, when it is at most the above upper limit, the photosensitive colored resin composition for color filters of the present invention can be used as a highly sensitive photosensitive colored resin composition for color filters.

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

<Blending ratio of each component in the photosensitive colored resin composition for color filters>
The total content of the color materials is preferably 3 to 65% by mass, more preferably 4 to 60% by mass, based on the total solid content of the photosensitive colored resin composition for color filters. When it is at least the above lower limit value, the colored layer has a sufficient color density when the photosensitive colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). Further, when it is at most the above upper limit value, it is possible to obtain a colored layer which is excellent in storage stability and has sufficient hardness and adhesion to a substrate. In the case of forming a coloring layer having a particularly high coloring material concentration, the content of the coloring material is 15 to 65% by mass, more preferably 25 to 65% by mass based on the total solid content of the photosensitive coloring resin composition for color filters. It is preferable to mix it in a proportion of 60% by mass.
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the color material, for example, relative to the total solid content of the color filter photosensitive colored resin composition. 1 to 40 mass% can be used. Further, it is preferably blended in a proportion of 2 to 30% by mass, and particularly preferably in a proportion of 3 to 25% by mass, based on the total solid content of the photosensitive colored resin composition for color filters. When it is at least the above lower limit value, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition for a color filter is excellent. When the content is at most the above upper limit, the strength of the colored layer will be excellent.
Particularly when a colored layer having a high coloring material concentration is formed, the content of the dispersant is 2 to 25% by mass, more preferably 3 to 25% by mass based on the total solid content of the photosensitive colored resin composition for a color filter. It is preferable to add 20% by mass. In the case of a salt-type block copolymer, the mass of the dispersant is one or more compounds selected from the group consisting of the block copolymer before salt formation and the general formulas (1) to (3). Is the total mass of and.
Moreover, the content of the solvent may be appropriately set within a range in which the colored layer can be accurately formed. It is usually preferably in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass, based on the total amount of the photosensitive colored resin composition for a color filter containing the solvent. preferable. When the content of the solvent is within the above range, the coating property can be excellent.

<Method for producing photosensitive colored resin composition for color filter>
The method for producing the photosensitive colored resin composition for a color filter of the present invention is not particularly limited, and for example, the coloring material dispersion liquid of the present invention contains an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, if necessary. It can be obtained by adding other components accordingly and mixing using a known mixing means.

[Color filter]
A color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a photosensitive material for a color filter according to the present invention. It has a colored layer formed by hardening a colored resin composition.

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

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

The colored layer can be formed, for example, by the following method.
First, the above-described photosensitive colored resin composition for a color filter of the present invention is subjected to a transparent treatment described below 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 and a die coating method. Apply on a substrate to form a wet coating. Among them, the spin coating method and the die coating method can be preferably used.
Then, the wet coating film is dried using a hot plate, an oven or the like, and then exposed through a mask having a predetermined pattern, and a photopolymerization reaction of an alkali-soluble resin and a polyfunctional monomer is performed to cure the resin. Use as a coating film. Examples of the light source used for exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, an electron beam, and the like. 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 after the exposure to accelerate the polymerization reaction. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition for a color filter used, the thickness of the coating film, and the like.

Next, development processing is performed using a developing solution to dissolve and remove the unexposed portion to form a coating film in a desired pattern. As the developer, a solution prepared by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. A general method can be adopted as the developing method.
After the development treatment, the colored layer is usually formed by washing the developing solution and drying the cured coating film of the photosensitive colored resin composition for color filters. After the development treatment, heat treatment may be performed to sufficiently cure the coating film. The heating condition is not particularly limited and is appropriately selected depending on the application of the coating film.

(Shading part)
The light-shielding portion in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and may 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 stripe shape and a matrix shape. The light shielding portion may be a thin metal film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light shielding portion may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, etc. is there.

The thickness of the light-shielding portion is set to about 0.2 to 0.4 μm in the case of a metal thin film, and set to about 0.5 to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin. To be done.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. There are materials.
The thickness of the transparent substrate is not particularly limited, but depending on the application of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used.
The color filter of the present invention is formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, and columnar spacers, in addition to the transparent substrate, the light-shielding portion, and the colored layer. May be.

[Liquid crystal display]
A liquid crystal display device of the present invention is characterized by including the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30 and 30.
The liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2 and may have a known structure as a liquid crystal display device that generally uses a color filter.

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

As a method for forming the liquid crystal layer, a method generally used as a method for 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 a counter substrate, and the liquid crystal is heated to be an isotropic liquid, and the liquid crystal cell is made to be an isotropic liquid by utilizing the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Then, the enclosed liquid crystal can be aligned by gradually 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 an isotropic phase, 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 stacking the color filter and the counter substrate together under reduced pressure and adhering them through a sealant. Then, the enclosed liquid crystal can be aligned by gradually cooling the liquid crystal cell to room temperature.

[Organic light emitting display]
An organic light emitting display device according to the present invention is characterized by including the color filter according to the present invention described above and an organic light emitting body.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitting body 80. The organic protective layer 50 and the inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitting body 80.

As a method of laminating the organic light emitting body 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which the organic light emitting body 80 formed on another substrate is attached to the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other structures in the organic light emitting body 80, known structures can be appropriately used. The organic light-emitting display device 100 manufactured in this manner is applicable to, for example, a passive drive type organic EL display and an active drive type organic EL display.
The organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3, and may have a publicly known structure as a general organic light emitting display device using a color filter.

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

Further, the glass transition temperature (Tg) of the block copolymer before salt formation was calculated by the following formula.
1/Tg=Σ(Xi/Tgi)
Here, it is assumed that the block copolymer is a copolymer of n monomer components from i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum of i=1 to n. As the value (Tgi) of the homopolymer glass transition temperature of each monomer, the value of Polymer Handbook (3rd Edition) (J. Brandrup, EH Immergut (Wiley-Interscience, 1989)) was adopted. The values (Tgi) of the homopolymer glass transition temperature of each monomer specifically used in Examples and Comparative Examples are as follows.
2-Hydroxyethyl methacrylate (HEMA): 55°C
2-Ethylhexyl methacrylate (EHMA): -10°C
N-Butyl methacrylate (BMA): 20°C
Benzyl methacrylate (BzMA): 54°C
Methyl methacrylate (MMA): 105°C
Methacrylic acid (MAA): 185°C
Dimethylaminoethyl methacrylate (DMMA): 18°C
Dimethylaminopropyl methacrylamide (DMAPMA): 96°C
Dimethylaminopropyl acrylamide (DMAPAA): 134°C
2-Hydroxy-3-phenoxypropyl acrylate (HPhPA) (trade name: M-600A, Kyoeisha Chemical Co., Ltd.): 17° C.
Methoxy polyethylene glycol (45) methacrylate (M-450G) (trade name: NK ester M-450G, Shin-Nakamura Chemical Co., Ltd.)
The glass transition temperatures of the block copolymers A-2 and A-3 of the following synthesis examples and the block copolymer A-16 of the comparative examples were calculated by the above method. 2, 67° C. (DSC measured value 69° C.), 65° C. (DSC measured value 66° C.) for block copolymer A-3, and 23° C. (DSC measured value) for block copolymer A-16. 23° C.), and it was shown that it was almost the same as the DSC measurement value.

(Synthesis Example 1: Production of Block Copolymer A-1)
In a 500 mL round-bottom four-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and dimethylketenemethyltrimethylsilylacetal as an initiator, 5.81. Parts by mass were added through an addition funnel, and nitrogen substitution was carried out sufficiently. 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of HEMA as a monomer for B block, 7.5 parts by mass of EHMA, 12.9 of BMA. Mass parts, BzMA10.7 mass parts, and MMA30.9 mass parts were dripped using the addition funnel over 60 minutes. The temperature was kept below 40° C. by cooling the reaction flask with an ice bath. After 1 hour, 18.3 parts by mass of DMAPMA, which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain an A block containing a structural unit represented by the general formula (I) and a B block having a hydrophilic property. To obtain a block copolymer A-1 (amine value 60 mg KOH/g, Tg 64° C.). The weight average molecular weight Mw was 7,600.

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

(Synthesis Example 6: Production of Block Copolymer A-6)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round bottom 4-neck separable flask equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and nitrogen substitution was performed sufficiently. It was After cooling the reaction flask to −60° C., 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 0.4 parts by mass of 1-ethoxyethyl methacrylate (EEMA) as a monomer for B block, 19.7 parts by mass of HEMA, 7.5 parts by mass of EHMA, 12.9 parts by mass of BMA, 10.7 parts by mass of BzMA, and 30.7 parts by mass of MMA. , Was added dropwise using an addition funnel over 60 minutes. After 30 minutes, 18.3 parts by mass of DMAPMA, which is a monomer for A block, which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solid content 30% solution. Water was added in an amount of 32.5 parts by mass, the temperature was raised to 100° C., and the reaction was carried out for 7 hours to deprotect the structural unit derived from EEMA to obtain a structural unit derived from methacrylic acid (MAA). The resulting block copolymer PGMEA solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain a block containing a structural unit represented by the general formula (I) and a structural unit derived from a carboxy group-containing monomer. To obtain a block copolymer A-6 containing B block having a solvent-solvent property (amine value 60 mgKOH/g, Tg 64° C., acid value 1 mgKOH/g). The weight average molecular weight Mw was 7,000.

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

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

(Synthesis Example 19: Synthesis of graft copolymer A-19)
(1) Preparation of macromonomer 160.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was charged into a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and nitrogen was charged. While stirring under a stream of air, the temperature was raised to 90°C. HEMA 39.4 parts by mass, EHMA 15.0 parts by mass, BMA 25.8 parts by mass, BzMA 21.4 parts by mass, MMA 61.8 parts by mass, 2-mercaptoethanol 8.0 parts by mass, PGMEA 60 parts by mass, α,α′-azo. A mixed solution of 2.0 parts by mass of bisisobutyronitrile (abbreviation AIBN) was added dropwise over 1.5 hours, and the mixture was further reacted for 3 hours. Next, the nitrogen stream was stopped, this reaction solution was cooled to 80° C., and 17.48 parts by mass of Karens MOI (manufactured by Showa Denko KK), 0.25 parts by mass of dibutyltin dilaurate, p-methoxyphenol. A macromonomer solution was obtained by adding 0.25 parts by mass and 20 parts by mass of PGMEA and stirring for 3 hours. The obtained macromonomer solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain macromonomer A. The weight average molecular weight Mw of the obtained macromonomer A was 4000.
(2) Preparation of Graft Copolymer A reactor equipped with a cooling pipe, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer was charged with 85.0 parts by mass of PGMEA, and the temperature was maintained while stirring under a nitrogen stream. Warmed to 85°C. The mixed solution of 87.8 parts by mass of macromonomer A prepared in (1), 18.3 parts by mass of DMAPMA, 1.24 parts by mass of n-dodecylmercaptan, 20.0 parts by mass of PGMEA, and 0.5 parts by mass of AIBN is 1.5 parts by mass. After dropping over a period of time and stirring with heating for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA is added dropwise over 10 minutes, followed by aging at the same temperature for 1 hour to obtain a graft copolymer. An A-19 solution was obtained. The macromonomer A has a mass ratio of HEMA:EHMA:BMA:BzMA:MMA (19.7:7.5:12.9:10) similar to that of the block copolymer A-1 with respect to 18.3 parts by mass of DMAPMA. 7:30.9 (parts by mass)).
The resulting graft copolymer A-19 solution was reprecipitated in hexane, filtered and purified by vacuum drying. The obtained graft copolymer A-19 had an amine value of 60 mgKOH/g, Tg of 64° C. and a weight average molecular weight of Mw12000.

(Synthesis Example 20: Synthesis of graft copolymer A-20)
(1) Preparation of Macromonomer In Synthesis Example 19, regarding the monomer ratio when preparing the macromonomer, 39.4 parts by mass of HEMA, 34.0 parts by mass of EHMA, 14.0 parts by mass of 15.0 parts by mass, and 25.8 parts of BMA. In the same manner as the macromonomer A, except that the mass part was changed to 24.0 parts by mass, BzMA 21.4 parts by mass to 20.0 parts by mass, and MMA61.8 parts by mass to 38.4 parts by mass, the macromonomer A was prepared. Monomer B was prepared. The weight average molecular weight Mw of the obtained macromonomer B was 4,100.
(2) Preparation of Graft Copolymer In Synthesis Example 19, the ratio of macromonomer and DMAPMA in preparing a graft copolymer was changed to 71.6 parts by mass of macromonomer B and 33.4 parts by mass of DMAPMA. Except for the above, a graft copolymer A-20 was synthesized in the same manner as in Synthesis Example 19. The macromonomer B was used in a mass ratio (18.4:7.0:12.0) of HEMA:EHMA:BMA:BzMA:MMA similar to that of the block copolymer A-3 with respect to 33.4 parts by mass of DMAPMA. :10.0:19.2 (parts by mass)). Table 1 shows the amine value, Tg, weight average molecular weight Mw, and acid value of the obtained graft copolymer.

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

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

Moreover, since phenylphosphonic acid is a divalent acid, the amine value and acid value of the salt block copolymer A-26 were specifically calculated as follows.
First, in the same manner as in Synthesis Example 1, a block copolymer A-1 (the block copolymer before salt formation of the salt-type block copolymer A-26 and the block copolymer A-1 are the same) is synthesized. did.
In a 100 mL round bottom flask, 10.0 parts by mass of the block copolymer A-1 was dissolved in 45.4 parts by mass of PGMEA, and the compound represented by the general formula (3) was phenylphosphonic acid (manufactured by Tokyo Kasei). Add 1.35 parts by mass (0.80 mol of the compound represented by the general formula (3) to 1 mol of the DMAPMA unit of the block copolymer A-1), and stir at a reaction temperature of 30° C. for 20 hours. Thus, a salt-type block copolymer A-26 solution having a solid content of 20 mass% was obtained.
Phenylphosphonic acid is a divalent acid, and since the acidic groups are present in excess of those used for salt formation, the acid value of the block copolymer after salt formation is higher than that of the block copolymer A-1. Specifically, the amine value after salt formation was calculated as follows.
1 g of a solution prepared by mixing 9 parts by mass of the salt block copolymer A-26 (solid substance after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was put into an NMR sample tube, and the 13 C-NMR spectrum was analyzed by nuclear magnetic resonance. Using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was carried out under the conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, at the terminal nitrogen site (amino group), the integrated value of the carbon atom peak adjacent to the non-salt-forming nitrogen atom and the carbon atom peak adjacent to the salt-forming nitrogen atom From the ratio, the ratio of the number of salt-forming amino groups to the total number of amino groups was calculated, and it was confirmed that all amino groups were salt-forming.
Since the amino group of DMAPMA without salt formation does not exist, the amine value after salt formation was calculated to be 0 mgKOH/g.
Since all of the amino groups of DMAPMA of the block copolymer A-1 form a salt with phenylphosphonic acid, 62.5% of all the phenylphosphonic acids have 1 molecule of phenylphosphonic acid. The remaining 37.5% of phenylphosphonic acid forms a salt with two amino acid groups in one molecule of DMAPMA, and the remaining 37.5% of phenylphosphonic acid forms a salt with one of the two acidic groups free (as an acid value). It is a calculated state). The acid value of the block copolymer before salt formation is 0 mgKOH/g, the acid value of phenylphosphonic acid measured by the method described in JIS K 0070 is 96 mgKOH/g, and the amine value consumed by salt formation is Since it was 60 mgKOH/g, the acid value after salt formation was calculated as 0+96-60=36 mgKOH/g. The measurement result of Tg of the salt-type block copolymer was 76°C.

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

(Synthesis Example 32: Synthesis of salt-type random copolymer A-32)
The (3-(N,N-dimethylamino)propylacrylamide/methoxy polyethylene glycol (45) methacrylate copolymer described in Production Example 1 of Patent Document 1 (International Publication No. 2014/10687) was prepared according to Patent Document 1 (International The salt type random copolymer A-32 solution was obtained by synthesis with reference to the description of Production Example 1 in JP 2014/10687 A. Specifically, it was prepared as follows.
In a 500 mL round bottom 4-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 45 parts by mass of PGMEA, 7.0 parts by mass of DMAPAA, and 23 parts of M-450G were used. 0.0 parts by mass and 0.09 parts by mass of 2-mercaptoethanol were added through a funnel for addition, and the atmosphere was sufficiently replaced with nitrogen. After heating to 78° C. under a nitrogen atmosphere, 16.3 parts by mass of DMAPAA, 55.0 parts by mass of M-450G, 0.21 part by mass of 2-mercaptoethanol, 105.0 parts by mass of PGMEA, and initiator 2 2.0 mass parts of 2,2-azobis-(2,4-dimethylvaleronitrile) was continuously added dropwise over 3 hours. After the dropping, a solution prepared by dissolving 0.25 parts by mass of 2,2-azobis-(2,4-dimethylvaleronitrile) in 2.5 parts by mass of PGMEA was added, and the reaction was continued at 78° C. for 1 hour. Further, a solution prepared by dissolving 0.25 parts by mass of 2,2-azobis-(2,4-dimethylvaleronitrile) in 2.5 parts by mass of PGMEA was added, and the reaction was continued for 1 hour at 78° C. to continue the copolymer solution. (Amine number 83 mg KOH/g) was obtained. The weight average molecular weight Mw was 17,900. After adding 150.0 parts by mass of the obtained copolymer solution to another 500 mL round-bottom 4-neck separable flask, nitrogen substitution was performed. Further, a solution prepared by dissolving 2.95 parts by mass of dimethylsulfate in 30.0 parts by mass of PGMEA (the number of moles of dimethylsulfate for 1 mol is 0.27 per 1 mol of the nitrogen site at the end of DMAPAA) was added dropwise, and at 85°C under a nitrogen atmosphere. The reaction was carried out for 3 hours. The obtained salt-type copolymer solution was reprecipitated in hexane, filtered and purified by vacuum drying to obtain a salt-type random copolymer A-32 (Tg-23°C).

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

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

(Synthesis Example 41: Synthesis of salt-type graft copolymer A-41)
The salt-type graft copolymer described in Production Example 11 of Patent Document 2 (Japanese Patent Laid-Open No. 2013-250446) is synthesized with reference to Synthesis Example 9 and Production Example 11 of Patent Document 2, and salt-type graft copolymerization is performed. A combined A-41 solution was obtained. Specifically, it was prepared as follows.
(1) Synthesis of macromonomer A reactor equipped with a cooling pipe, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer was charged with 160.0 parts by mass of PGMEA and stirred at a temperature of 90° C. under a nitrogen stream. Warmed to. A mixed solution of MMA 100.0 parts by mass, BMA 60.0 parts by mass, BzMA 40.0 parts by mass, 2-mercaptoethanol 8.0 parts by mass, PGMEA 60 parts by mass, AIBN 2.0 parts by mass was added dropwise over 1.5 hours, The reaction was continued for another 3 hours. Next, the nitrogen stream was stopped, this reaction solution was cooled to 80° C., and 17.48 parts by mass of Karens MOI (manufactured by Showa Denko KK), 0.25 parts by mass of dibutyltin dilaurate, p-methoxyphenol. A macromonomer was obtained by adding 0.25 parts by mass and 20 parts by mass of PGMEA and stirring for 3 hours. The obtained macromonomer solution was reprecipitated in hexane, filtered and purified by vacuum drying to obtain macromonomer C. The weight average molecular weight Mw of the obtained macromonomer C was 4000.
(2) Synthesis of Graft Polymer A reactor equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer was charged with 129.8 parts by mass of PGMEA, and the temperature was adjusted to 85 while stirring under a nitrogen stream. Warmed to °C. 13.4 parts by mass of the macromonomer C33.4 parts by mass, DMAPAA (manufactured by Kojin Co., Ltd.) 16.7 parts by mass, n-dodecyl mercaptan 1.24 parts by mass, PGMEA 20.0 parts by mass, AIBN 0.5 parts by mass. After adding dropwise over 5 hours and stirring under heating for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA is added dropwise over 10 minutes, and further aged at the same temperature for 1 hour to prepare a graft copolymer. A polymer solution was obtained. The obtained graft copolymer solution was reprecipitated in hexane, filtered and purified by vacuum drying. The obtained graft copolymer had an amine value of 122 mgKOH/g and a weight average molecular weight Mw11200.
(3) Synthesis of Salt-type Graft Copolymer A-41 In a 100 mL round bottom flask, 10.0 parts by mass of the above graft copolymer was dissolved in 63.15 parts by mass of PGMEA and represented by the general formula (3). 2-methacryloyloxyethyl acid phosphate (trade name: light ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.), 5.78 parts by mass (the compound represented by the general formula (3) is a graft copolymer). 1.0 mol) was added to 1 mol of the combined DMAPAA units, and the mixture was stirred at a reaction temperature of 40° C. for 20 hours to give a salt-type graft copolymer A-41 (Tg 80° C.) solution having a solid content of 20% by mass. Obtained.
Since the light ester P-2M is a monovalent acid and the acidic group is used for salt formation, the acid value of the graft copolymer after salt formation is the same as that of the graft copolymer before salt formation. The amine value after salt formation was calculated as follows.
1 g of a solution prepared by mixing 9 parts by mass of the salt-type graft copolymer A-41 (solid substance after reprecipitation) and 91 parts by mass of chloroform-D1 NMR was put into an NMR sample tube, and the 13 C-NMR spectrum was analyzed by nuclear magnetic resonance. Using an apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), the measurement was carried out under the conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, at the terminal nitrogen site (amino group), the integrated value of the carbon atom peak adjacent to the non-salt-forming nitrogen atom and the carbon atom peak adjacent to the salt-forming nitrogen atom From the ratio, the ratio of the number of salt-forming amino groups to the total number of amino groups was calculated, and it was confirmed that all amino groups were salt-forming. Since no amino group of DMAPAA that does not form a salt exists, the amine value after salt formation was calculated to be 0 mgKOH/g.

(Synthesis Example 42: Synthesis of alkali-soluble resin A solution)
In a polymerization tank, 300 parts by mass of PGMEA was charged, and after heating to 100° C. under a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA) and perbutyl. 6 parts by mass of O (manufactured by NOF CORPORATION) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Then, the reaction was continued at 100° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the dropping of the main chain-forming mixture to terminate the polymerization.
Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110° C., 0.8 parts by mass of triethylamine was added, and the mixture was heated at 110° C. for 15 hours. An addition reaction was performed to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass).
The weight average molecular weight of the alkali-soluble resin was measured by using a polystyrene as a standard substance and THF as an eluent using a Shodex GPC System-21H. The acid value was measured according to JIS K0070.

(Example 1)
(1) Production of color material dispersion G-1
1.95 parts by mass of the block copolymer A-1 of Synthesis Example 1 was used as the dispersant, and C.I. I. Pigment Green 58 (PG58) 13.0 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 42 16.25 parts by mass, PGMEA 68.8 parts by mass, particle size 2.0 mm zirconia beads 100 parts by mass. Was placed in a mayonnaise bottle and shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as preliminary crushing, and then zirconia beads having a particle diameter of 2.0 mm were taken out and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were taken out. In the same manner, the main crushing was performed and the mixture was dispersed for 4 hours with a paint shaker to obtain a color material dispersion liquid G-1.

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

(Examples 2 to 24)
(1) Production of Coloring Material Dispersions G-2 to G-24 In (1) of Example 1, instead of the block copolymer A-1, as shown in Tables 3 to 4, Synthesis Example 2 was used. 3 to 3 block copolymers A-2 to A-3, synthesis examples 6 to 15 block copolymers A-6 to A-15, and synthesis examples 21 to 31 salt-type block copolymers A-21 to A -31 solution was used so that the solid content was the same as that of the block copolymer A-1, and the PGMEA amount was adjusted so that the total amount was 100 parts by weight. In the same manner, color material dispersions G-2 to G-24 were obtained.
(2) Production of Photosensitive Colored Resin Compositions G-2 to G-24 for Color Filter In (2) of Example 1, instead of the color material dispersion liquid G-1, the above color material dispersion liquid G-2 was used. To G-24 were used, and photosensitive colored resin compositions G-2 to G-24 for color filters were obtained in the same manner as in (2) of Example 1.

(Comparative Examples 1 to 17)
(1) Production of Comparative Coloring Material Dispersions CG-1 to CG-17 In (1) of Example 1, instead of the block copolymer A-1, as shown in Tables 3 to 4, synthetic examples Block copolymers A-4 and A-5 of Nos. 4 and 5, block copolymers A-16 to A-18 of Synthesis Examples 16 to 18 and graft copolymers A-19 to A- of Synthesis Examples 19 to 20. 20, salt type random copolymer A-32 of Synthesis Example 32, salt type block copolymers A-33 to A-36 solutions of Synthesis Examples 33 to 36, salt type graft copolymer A of Synthesis Examples 37 to 41 -37 to A-41 solutions were used so that the solid content was the same as that of the block copolymer A-1, respectively, and the PGMEA amount was adjusted so that the total amount was 100 parts by weight. Comparative color material dispersions CG-1 to CG-17 were obtained in the same manner as in (1).
(2) Production of Photosensitive Colored Resin Compositions CG-1 to CG-17 for Comparative Color Filter In (2) of Example 1, instead of the color material dispersion liquid G-1, the comparative color material dispersion liquid CG was used. Photosensitive colored resin compositions CG-1 to CG-17 for comparative color filters were obtained in the same manner as in (2) of Example 1 except that -1 to CG-17 were used.

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

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

(Contrast evaluation standard)
A: Green exceeds 7300, Red exceeds 4000, Blue exceeds 6800 B: Green exceeds 6600, 7300 or less, Red exceeds 3300, 4000 or less, Blue exceeds 6100, 6800 or less C: Green exceeds 5700, 6600 or less, Red exceeds 2600 Exceeding 3300 or less, Blue is 5400 Exceeding 6100 or less D: Green is 5700 or less, Red is 2600 or less, Blue is 5400 or less However, in each C light source, Green is y=0.500, Red is x=0.650, Blue is It is a value when y=0.135.
Even if the evaluation result is B, the color filter photosensitive colored resin composition can be practically used, but if the evaluation result is A, the color filter photosensitive colored resin composition is suitable for further increasing the contrast.

<Development adhesion evaluation>
The photosensitive colored resin compositions for color filters obtained in Examples and Comparative Examples were each spun on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm×100 mm. After the post-baking using a coater, the colored layer having a thickness of 1.6 μm was formed and then dried at 80° C. for 3 minutes using a hot plate to form the colored layer. This colored layer was irradiated with 60 mJ/cm ² of ultraviolet rays through a photomask having a mask opening width of ² to 80 μm using an ultrahigh pressure mercury lamp. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkaline developer. The substrate after development was observed with an optical microscope to observe the presence or absence of the colored layer with respect to the mask opening line width. The results are also shown in Tables 3 and 4.
(Development adhesion evaluation criteria)
A: A colored layer was observed in a portion with a mask opening line width of less than 20 μm B: A colored layer was observed in a portion with a mask opening line width of 20 μm or more and less than 50 μm C: A portion of the mask opening line width of 50 μm or more, less than 80 μm A colored layer was observed in D: No colored layer was observed in a portion having a mask opening line width of 80 μm or less. Even if the evaluation result is B, the photosensitive colored resin composition for color filter can be practically used, but the evaluation result is A. Then, the photosensitive colored resin composition for color filters is suitable for higher definition.

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

<Solvent resolubility evaluation>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was dipped in the photosensitive colored resin composition for color filter obtained in Examples and Comparative Examples, and applied to a 1 cm long portion of the glass substrate. The pulled glass substrate was placed in a thermo-hygrostat so that the glass surface was horizontal, and dried at a temperature of 23° C. and a humidity of 80% RH for 30 minutes. Next, the glass substrate with the dried coating film was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dried coating film was visually determined and evaluated. The results are also shown in Tables 3 and 4.
(Solvent resolubility evaluation criteria)
A: The dry coating film was completely dissolved B: Dry coating flakes were formed in the solvent and the solution was colored C: Dry coating flakes were formed in the solvent, and the solution was not colored D: In the solvent No flakes of the dried coating film were formed on the surface of the coating solution, and the solution was not colored.

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

On the other hand, in Comparative Example 1 in which the glass transition temperature of the dispersant is 30° C. or higher, but the amine value is lower than the specific value of the present application, the colorant dispersion stability is poor, and the contrast of the colored layer is poor. Further, the development residue was outside the practical level range. Further, in Comparative Example 2 in which the glass transition temperature of the dispersant was 30° C. or higher, but the amine value was higher than the specific value of the present application, the solvent resolubility was outside the practical level range.
Further, it was revealed that Comparative Example 3 in which the glass transition temperature of the dispersant was less than 30° C. was inferior in development adhesion. Comparative Example 8 using the copolymer corresponding to Production Example 1 of Patent Document 1 also had a glass transition temperature of less than 30° C. and had poor development adhesion. Since the copolymer corresponding to Production Example 1 of Patent Document 1 is a random copolymer, it was also inferior in color material dispersion stability and inferior in contrast of the colored layer.
Comparative Example 4 in which a block copolymer or a salt-type block copolymer containing a constitutional unit derived from dimethylaminoethyl methacrylate instead of the constitutional unit represented by the general formula (I) was used as a dispersant, Nos. 5 and 9 to 12 were inferior in color material dispersion stability and inferior in contrast of the coloring layer.
In addition, Comparative Examples 6, 7, 13 to 17 each containing the constitutional unit represented by the general formula (I) as a dispersant, but using a graft copolymer or a salt-type graft copolymer, all of the present inventions. The color material dispersion stability was inferior to that of Comparative Example 17 was also inferior in development adhesion and had an amine value higher than the specific value of the present application, so that the solvent redissolvability was outside the practical range.

Next, an experiment for examining the influence of the dispersant content on the shape and physical properties of the colored layer will be shown.
Table 5 compares the dispersion stability and the development residue, the evaluation of the coloring pattern chip shown below, and the water stain with the photosensitive color resin composition for a color filter of Example 1 described above. The results obtained with respect to the photosensitive colored resin compositions for color filters of Example 4, Comparative Example 6 and Comparative Example 7 are shown. In each of Example 1, Comparative Example 4, Comparative Example 6, and Comparative Example 7, D/P (mass ratio) is 0.15 when the dispersant content is D and the colorant content is P. Here is an example. The colorant dispersion stability evaluation of Example 1 is as high as A, whereas the colorant dispersion stability evaluations of Comparative Example 4, Comparative Example 6, and Comparative Example 7 are inferior as D and C, respectively. Since Example 1 and Comparative Examples 4, 6, and 7 have the same D/P ratio and the same other composition, the evaluation of the lack of the colored pattern and the evaluation of the water stain are the same. is there. On the other hand, in order to enhance the colorant dispersion stability of the dispersants of Comparative Examples 4, 6, and 7 to the same level as in Example 1, the following Comparative Examples 18, 19, and 20 were used. As shown, it was revealed that this could not be achieved without increasing the D/P ratio. However, it was clarified that when the D/P ratio was increased, the dispersion stability was increased, but the defectives of the coloring pattern, water stain, and development residue were all deteriorated.

(Comparative Example 18)
(1) Production of Comparative Coloring Material Dispersion CG-18 In (1) of Comparative Example 4, the block copolymer A- was prepared so that the D/P ratio was 0.35 while the amount of the coloring material remained the same. Comparative Color Material Dispersion Liquid CG-18 was obtained in the same manner as in (1) of Comparative Example 4 except that the content of 17 was increased and the PGMEA amount was adjusted so that the total amount became 100 parts by mass.
(2) Production of Photosensitive Colored Resin Composition CG-18 for Comparative Color Filter In (2) of Comparative Example 4, the above comparative color material dispersion liquid G-18 was used instead of the color material dispersion liquid CG-4. , 0.44 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.41 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and PGMEA of 7. A photosensitive colored resin composition CG-18 for a comparative color filter was obtained in the same manner as in (2) of Comparative Example 4 except that the amount was 05 parts by mass.

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

(Comparative Example 20)
(1) Production of Comparative Coloring Material Dispersion CG-20 In (1) of Comparative Example 7, the graft copolymer A- was prepared so that the D/P ratio was 0.25 while the amount of coloring material remained the same. Comparative Color Material Dispersion Liquid CG-20 was obtained in the same manner as in (1) of Comparative Example 7 except that the content of 20 was increased and the PGMEA amount was adjusted so that the total amount was 100 parts by mass.
(2) Production of Photosensitive Colored Resin Composition G-20 for Comparative Color Filter In (2) of Comparative Example 7, the above-mentioned comparative color material dispersion liquid G-20 was used instead of the color material dispersion liquid CG-7. 0.56 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.52 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and PGMEA of 6. A photosensitive colored resin composition CG-20 for a comparative color filter was obtained in the same manner as in (2) of Comparative Example 7 except that the amount was 84 parts by mass.

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

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

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

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

<Evaluation of lack of colored pattern>
The photosensitive colored resin compositions obtained in Examples and Comparative Examples were post-baked with a spin coater on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) to a thickness of 1. After coating to a thickness of 6 μm to form a colored layer, it is dried at 80° C. for 3 minutes using a hot plate, and the colored layer is passed through a photomask having a stripe-shaped mask opening width of 90 μm, and then an ultra-high pressure mercury lamp. Was used to expose a colored layer on the glass substrate by exposing it to ultraviolet light of 30 mJ/cm ² . Then, 0.05 wt% potassium (KOH) is spin-developed as a developing solution, the developing solution is indirectly treated for 60 seconds, and then washed with pure water to perform development processing, thereby forming a pattern with a line width as shown below. did.
Using an optical microscope, the edges of the colored pattern formed on the glass substrate after exposure and development were observed to evaluate the lack of the colored pattern.
(Evaluation criteria)
A: No color pattern chipping was observed B: Coloring pattern chipping was slightly observed C: Coloring pattern chipping was observed many D: Coloring pattern chipping was observed significantly many Coloring pattern chipping When the evaluation criterion is A or B, it is evaluated that the chipping of the colored pattern is sufficiently suppressed, and it can be used practically without any problem.

<Water stain evaluation>
The photosensitive colored resin compositions obtained in Examples and Comparative Examples were post-baked with a spin coater on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) to a thickness of 1. After coating to a thickness of 6 μm to form a colored layer, it is dried at 80° C. for 3 minutes using a hot plate, and 60 mJ/cm ² of ultraviolet light is entirely irradiated using a super high pressure mercury lamp without a photomask. Thus, a colored layer was formed on the glass substrate. Then, 0.05 wt% potassium (KOH) is spin-developed as a developing solution, the developing solution is indirectly treated with the developing solution for 60 seconds, and then washed with pure water to perform a development treatment. Immediately after removal by centrifugation, the contact angle of pure water was measured as described below to evaluate water stain. It should be noted that if the contact angle of pure water is 65 degrees or more, it is evaluated that no water stain, which causes a problem of irregularity in the appearance inspection, will occur.
The contact angle of pure water was measured by dropping 1.0 μL of pure water onto the surface of the colored layer immediately after the water was removed by centrifugation, and measuring the static contact angle 10 seconds after the deposition according to the θ/2 method. Measured. The measurement was performed using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd.
(Evaluation criteria)
A: Contact angle of 80 degrees or more B: Contact angle of 65 degrees or more and less than 80 degrees C: Contact angle of 50 degrees or more and less than 65 degrees D: Contact angle of less than 50 degrees Water stain is sufficient if the evaluation criteria is A or B. It is evaluated that it is suppressed to, and it can be used without any practical problems.

[Summary of results]
In order to increase the colorant dispersion stability of the dispersants of Comparative Examples 4, 6, and 7 to the same level as in Example 1, as shown in Comparative Examples 18, 19, and 20 below. It was revealed that it could not be achieved unless the D/P ratio was increased. As described above, in the conventional dispersant, when the dispersant content is increased to such an extent that the colorant dispersion stability becomes good, the colorant dispersion stability becomes as excellent as that of the present invention, but the photosensitive coloring It was clarified that the content of the binder component contained in the resin composition had to be relatively low, resulting in problems such as chipping of the coloring pattern and water stains.
In addition, Example 25 and Example 26 in which an oxime ester-based photoinitiator was used instead of the photoinitiator used in Example 1 had a high effect of suppressing the occurrence of a colored pattern chip or water stain. Was revealed. Similarly, in Comparative Example 21 and Comparative Example 22 using the oxime ester photoinitiator, compared to Comparative Example 18, Comparative Example 19 and Comparative Example 20 in which the oxime ester photoinitiator was not used, the coloring pattern was lacking. Although the occurrence of water stain was reduced, it was revealed that the effect was inferior to the effect of the present invention.

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

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

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

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

(Example 28)
(1) Production of color material dispersion B-1
1.95 parts by mass of the salt-type block copolymer A-27 of Synthesis Example 27 (benzyl bromide 0.2 molar equivalent) as a dispersant, and C.I. I. Pigment Blue 15:6 (PB15:6) is 13.0 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 42 is 16.25 parts by mass, PGMEA is 68.8 parts by mass, and the particle size is 2.0 mm zirconia. Put 100 parts by mass of beads in a mayonnaise bottle, shake for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) as preliminary crushing, then take out zirconia beads having a particle size of 2.0 mm and make zirconia particles having a particle size of 0.1 mm. 200 parts by mass of beads were added, and similarly the main disintegration was performed and dispersed for 4 hours with a paint shaker to obtain a color material dispersion liquid B-1.

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

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

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

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

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

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

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

(Comparative Example 28)
(1) Production of color material dispersion liquid CR-2
In Comparative Example 27 (1), the content of the salt-type block copolymer A-35 was increased so that the D/P ratio was 0.35 while the amount of the color material was the same, and the total was 100. Comparative Coloring Material Dispersion Liquid CR-2 was obtained in the same manner as in (1) of Comparative Example 27, except that the PGMEA amount was adjusted to be parts by mass.
(2) Production of Photosensitive Colored Resin Composition CR-2 for Comparative Color Filter In (2) of Comparative Example 27, the above-mentioned comparative color material dispersion liquid CR-2 was used instead of the color material dispersion liquid CR-1. , 0.44 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 42, 0.41 parts by mass of a polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), and PGMEA of 7. A photosensitive colored resin composition CR-2 for a comparative color filter was obtained in the same manner as in (2) of Comparative Example 27 except that the amount was changed to 05 parts by mass.

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

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

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

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

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

[Summary of results]
From the results of Table 7, the coloring material dispersions of Examples 29 to 30 using the salt type block copolymer containing the constitutional unit represented by the general formula (I) specified in the present invention as the dispersant It was revealed that the coloring material dispersion stability was excellent. Further, the photosensitive color resin composition for a color filter of Examples 29 to 30 prepared using the color material dispersion liquid of Examples 29 to 30 is excellent in color material dispersion stability and excellent in contrast, and It was revealed that the effect of suppressing the precipitation of pigment aggregates is high after the heating step after fine dispersion.

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

(Examples 2 to 10, Reference Example 11, Examples 12 to 24)
(1) Production of Coloring Material Dispersions G-2 to G-24 In (1) of Example 1, instead of the block copolymer A-1, as shown in Tables 3 to 4, Synthesis Example 2 was used. 3 to 3 block copolymers A-2 to A-3, synthesis examples 6 to 15 block copolymers A-6 to A-15, and synthesis examples 21 to 31 salt-type block copolymers A-21 to A -31 solution was used so that the solid content was the same as that of the block copolymer A-1, and the PGMEA amount was adjusted so that the total amount was 100 parts by weight. In the same manner, color material dispersions G-2 to G-24 were obtained.
(2) Production of Photosensitive Colored Resin Compositions G-2 to G-24 for Color Filter In (2) of Example 1, instead of the color material dispersion liquid G-1, the above color material dispersion liquid G-2 was used. To G-24 were used, and photosensitive colored resin compositions G-2 to G-24 for color filters were obtained in the same manner as in (2) of Example 1.

[Summary of results]
From the results of Tables 1 to 4, the block copolymer (P1) containing the constitutional unit represented by the general formula (I) as the dispersant, and the general formula (I) of the block copolymer are used. A salt in which at least a part of the terminal nitrogen moiety of the structural unit represented by the formula and one or more compounds selected from the group consisting of compounds represented by the following general formulas (1) to (3) form a salt. Dispersant which is at least one type of block copolymer (P2), wherein the block copolymer (P1) has an amine value of 35 to 110 mgKOH/g, and the glass transition temperature of the dispersant is 30°C or higher. It is clear that the coloring material dispersion liquids of Examples 1 to 10, Reference Example 11, and Examples 12 to 24 using are excellent in coloring material dispersion stability even when the amount of the dispersant is reduced. became. It is considered that the dispersant containing the constitutional unit represented by the general formula (I) of the present application has a high basicity at the terminal nitrogen site and a strong adsorptivity to the coloring material.
Also the Example 1-10, Example 11, Example 12 to Examples 1 10 were prepared using the colorant dispersion liquid 24, Reference Example 11, the photosensitive coloring color filters of Examples 12 to 24 The resin composition was excellent in the dispersibility of the coloring material and thus was excellent in the contrast of the colored layer, and was further excellent in the development adhesion and the solvent re-dissolvability while suppressing the generation of the development residue.
Comparison between Reference Example 11 and Examples 1 to 10, 12 and 13 revealed that the development adhesion was improved in the case of a copolymer containing a structural unit derived from a hydroxyl group-containing monomer.
Among them, the photosensitive colored resin compositions for color filters of Examples 4 to 5 in which the block copolymer containing a structural unit having an acidic functional group is used in the B block which imparts the hydrophilic property are improved in the effect of suppressing the development residue. It was revealed to do.
Further, among them, the photosensitive colored resin compositions for color filters of Examples 14 to 24 using the salt-type block copolymer were particularly excellent in dispersibility of coloring material, and the contrast of the obtained colored layer was particularly excellent. ..
Particularly, in Examples 23 to 24, the acid value increased when a block copolymer containing a structural unit having an acidic functional group was used in the B block that imparts hydrophilicity, and the salt block copolymer was used. It was clarified that the photosensitive colored resin composition for a color filter has a further improved effect of suppressing development residues as compared with Example 5.

Claims (11)

A coloring material dispersion liquid containing a coloring material, a dispersant, and a solvent,
The dispersant is at least one of the following block copolymer (P1) and the following salt-type block copolymer (P2),
P1: a block copolymer containing a structural unit represented by the following general formula (I):
P2: From the compound represented by the following general formulas (1) to (3) and at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer (P1) A salt-type block copolymer in which a salt is formed with one or more compounds selected from the group consisting of:
A color material dispersion liquid for a color filter, wherein the block copolymer (P1) has an amine value of 35 to 110 mgKOH/g, and the dispersant has a glass transition temperature of 30° C. or higher.
(In the general formula (I), R ¹ and R ^1′ are each independently a hydrogen atom or a methyl group, A is an alkylene group having 1 to 8 carbon atoms, —[CH(R ⁶ )—CH(R ⁷ ). A divalent group represented by -O] _x -CH(R ⁶ )-CH(R ⁷ )- or [(CH ₂ ) _y- O] _z -(CH ₂ ) _y- , R ² and R ³ are Each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, and R ² and R ³ may be bonded to each other to form a ring structure, and R ⁶ and R ⁷ are each independently. It is a hydrogen atom or a methyl group, x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18.
In the general formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or —OR It represents ^e, R ^e is a straight chain of 1 to 20 carbon atoms, branched chain or cyclic alkyl group, a vinyl group, an optionally substituted phenyl group or a benzyl group, or an alkylene having 1 to 4 carbon atoms Represents a (meth)acryloyl group through a group. In the general formula (2), R ^b , R ^b′ , and R ^b″ each independently represent a hydrogen atom, an acidic group or its ester group, a straight chain having 1 to 20 carbon atoms which may have a substituent, It represents a branched or cyclic alkyl group, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -O- ^Rf , and ^Rf has a substituent. May be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a carbon number of 1 Represents a (meth)acryloyl group via an alkylene group of 4 to 4, X represents a chlorine atom, a bromine atom, or an iodine atom, In formula (3), R ^c and R ^d are each independently a hydrogen atom. Represents a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or —O—R ^e , and R ^e represents A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a (meth)acryloyl group having an alkylene group having 1 to 4 carbon atoms. Represents a group, provided that at least one of R ^c and R ^d contains a carbon atom.) The color material dispersion liquid for a color filter according to claim 1, wherein the color material includes one or more selected from the group consisting of phthalocyanine pigments, diketopyrrolopyrrole pigments, and quinophthalone pigments. The color material dispersion liquid for a color filter according to claim 1 or 2, wherein the block copolymer (P1) in the dispersant contains a structural unit derived from a hydroxyl group-containing monomer. The block copolymer (P1) in the dispersant is
(I) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer, and
(Ii) The color material dispersion liquid for a color filter according to any one of claims 1 to 3, which contains at least one structural unit derived from a monomer containing a hydroxyl group and an aromatic group. In the salt-type block copolymer (P2), the group consisting of the general formulas (1) to (3) with respect to 1 mol of the terminal nitrogen moiety contained in the structural unit represented by the general formula (I). The color material dispersion liquid for a color filter according to any one of claims 1 to 4, wherein 0.1 to 0.8 mol of one or more compounds selected from the above is contained. The block copolymer (P1) in the dispersant further contains a structural unit derived from a carboxy group-containing monomer, the block copolymer (P1) has an acid value of 1 to 18 mgKOH/g, and the salt form The color material dispersion liquid for a color filter according to any one of claims 1 to 5, wherein the block copolymer (P2) has an acid value of 1 to 55 mgKOH/g. A photosensitive colored resin composition for a color filter, which comprises the color material dispersion liquid according to any one of claims 1 to 6, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. The photosensitive colored resin composition for a color filter according to claim 7, wherein the photoinitiator contains an oxime ester. A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers cures the photosensitive colored resin composition for a color filter according to claim 7 or 8. A color filter having a colored layer formed by the above process. A liquid crystal display device comprising: the color filter according to claim 9; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate. An organic light emitting display device comprising the color filter according to claim 9 and an organic light emitting body.