CN107003448B

CN107003448B - Color material dispersion liquid, photosensitive colored resin composition, color filter, liquid crystal display device, and organic light-emitting display device

Info

Publication number: CN107003448B
Application number: CN201580065051.5A
Authority: CN
Inventors: 长井健朗; 中村和彦; 冢本力飞; 五十岚一贵; 上森理惠; 市川裕司
Original assignee: DNP Fine Chemicals Co Ltd
Current assignee: DNP Fine Chemicals Co Ltd
Priority date: 2014-12-24
Filing date: 2015-12-22
Publication date: 2020-02-14
Anticipated expiration: 2035-12-22
Also published as: TW201631051A; CN107003448A; TWI683864B

Abstract

Composition with excellent adhesion the color material dispersion liquid for a color filter of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent; the dispersant is at least 1 of the following block copolymer (P1) and the following salt-type block copolymer (P2); p1: a block copolymer having an A block containing a constituent unit represented by the following general formula (I) and a B block containing a constituent unit derived from a carboxyl group-containing monomer; p2: a salt-type block copolymer in which at least a part of the nitrogen sites at the ends of the constituent units represented by the general formula (I) of the block copolymer and 1 or more compounds selected from the group consisting of compounds represented by the following general formulae (1) to (3) form a salt; the acid value of the dispersant is 1-18 mgKOH/g, and the glass transition temperature of the dispersant is above 30 ℃.

(the symbols in the general formula (I) and the formulae (1) to (3) are as defined in the specificationLoad).

Description

Color material dispersion liquid, photosensitive colored resin composition, color filter, liquid crystal display device, and organic light-emitting display device

Technical Field

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

Background

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The popularity of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Recently, organic light emitting display devices such as organic EL displays, which use self-emission and have high visibility, have also been receiving attention as next-generation image display devices. In the performance of these image display apparatuses, further improvement in image quality such as improvement in contrast and color reproducibility, or reduction in power consumption is strongly desired.

The existing display devices are mostly based on the international standard sRGB (IEC61966-2-1) of the chromaticity space. However, in order to find a display closer to a real object and to further improve color reproducibility, there is an increasing demand for a display device compatible with AdobeRGB having a wider color gamut than sRGB. The AdobeRGB specification is defined by a chromaticity space proposed by Adobe Systems, and the three primary colors in AdobeRGB are determined by chromaticity coordinates x and y in an XYZ color system as described below. The AdobeRGB specification is characterized by a wider color gamut in the green direction than the sRGB specification.

Red: x is 0.64; y is 0.34

Green: x is 0.21; y is 0.71

Blue: x is 0.15; y is 0.06

In addition, a display device conforming to the dci (digital cinema initiatives) specification having a wider color gamut in the red and green directions than the sRGB is also required.

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, light passing through a color filter is directly colored into colors of respective pixels constituting the color filter, and the light of these colors is synthesized to form a color image. As the light source in this case, in addition to the conventional cold cathode ray tube, there are cases where an organic light emitting element emitting white light and an inorganic light emitting element emitting white light are used. In addition, in the organic light emitting display device, a color filter is used for color adjustment and the like.

In this case, demands for higher brightness, higher contrast, and improved color reproducibility in the color filter are also increasing.

Here, the color filter generally includes a transparent substrate, a colored layer formed on the transparent substrate and including a colored pattern of three primary colors of red, green, and blue, and a light shielding portion formed on the transparent substrate to partition each colored pattern.

Among the methods for forming pixels in a color filter, a pigment dispersion method having excellent average characteristics is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, accuracy, and the like.

In a color filter having pixels formed by a pigment dispersion method, the miniaturization of pigments has been studied in order to achieve higher brightness and higher contrast. It is considered that the fine pigment particles can reduce scattering of light passing through the color filter due to pigment particles, thereby achieving high brightness and high contrast.

However, the finely divided pigment particles are liable to agglomerate, and therefore, there is a problem that dispersibility or dispersion stability is lowered.

As a method for improving the dispersion method of a finely divided pigment, it is known that the use of a dispersant is effective. For example, patent document 1 discloses a color composition for a color filter using a block copolymer as a pigment dispersant, the block copolymer having: the A block having a specific repeating unit having an amino group or an ammonium salt group, and the B block having a specific repeating unit having an alkyleneoxy chain derived from an alcohol moiety of a carboxylic acid ester and a repeating unit having an acidic group.

Further, patent document 2 discloses a color composition for a color filter using a copolymer as a pigment dispersant, the copolymer containing: the resin composition comprises a specific repeating unit having an amino group or an ammonium salt group, a repeating unit containing a carboxylic acid ester, and a repeating unit having an acidic group, wherein the repeating unit containing a carboxylic acid ester is set to a specific ratio, and the ratio of the weight average molecular weight to the number average molecular weight is set to a specific ratio.

On the other hand, in the color filter, the 3-dot region connecting the red, green, and blue pixels is a limit of colors that can be reproduced. That is, the larger the triangle obtained by the 3 dots of the red, green, and blue pixels, the wider the range of colors reproducible on the screen by the display device.

In order to realize a wide color gamut space such as AdobeRGB or DCI, green pixels of the color filter are particularly required to have a high color density green color region "x is 0.14 to 0.30, y is 0.55 to 0.75)," preferably (x is 0.14 to 0.30, y is 0.57 to 0.75), and more preferably (x is 0.14 to 0.30, y is 0.61 to 0.75).

Examples of the Green pigment widely used for the Green pixel include c.i. pigment Green 7 (hereinafter, may be abbreviated as PG7), c.i. pigment Green 36 (hereinafter, may be abbreviated as PG36), and c.i. pigment Green 58 (hereinafter, may be abbreviated as PG 58).

However, when a green pixel is produced so as to realize the green region of high color density using PG7, there is a problem in that the luminance of the green pixel is reduced. When a green pixel is formed using PG7 as a main green color material, the color filter is dark.

When a green pixel is produced using PG36 so as to realize the green region having a high color density, the luminance of the green pixel is reduced, although not as much as PG 7.

In addition, although the luminance is high when PG58 is used, when a green pixel including the green region having a high color density is to be produced, the green pixel must be formed very thick, which is not only problematic in mass production, but also makes it difficult to maintain the color filter performance because only the green pixel is formed thick. Even if PG58 is used alone, the green region having a high color density is not realized, and there is a limit to the green pixel to be formed in a larger triangle.

Patent document 3 describes that a pigment containing high zinc phthalocyanine chloride is used as a colored resin composition for a color filter that realizes a target chromaticity of green with a high color density without increasing the thickness of the film and that can form a green pixel with high luminance. However, higher brightness is also required.

On the other hand, patent document 4 discloses a color filter coloring composition containing a pigment dispersant containing an amine polymer as a specific constituent unit and a block copolymer aggregation inhibitor containing a constituent unit having a 4-stage ammonium salt group in a side chain and a constituent unit having no 4-stage ammonium salt group as an aggregation inhibitor, in combination, with the object of providing a colored curable resin composition for a color filter in which occurrence of a foreign substance failure due to a zinc bromide phthalocyanine pigment which has recently been attracting attention as a green pixel formation pigment is suppressed. However, the zinc bromide phthalocyanine pigment described in patent document 4 is substantially only c.i. pigment green 58(PG58), and a green pigment dispersion exhibiting bluish green and high brightness cannot be obtained.

In addition, the green pixel has a problem that a display failure is likely to occur. More specifically, in the liquid crystal display device of the transverse electric field system, since a colored layer of a color filter is present in a liquid crystal driving electric field, the colored layer is greatly affected by the electric characteristics of the colored layer. When PG36 is used for the green pixel, various display defects such as liquid crystal alignment disorder due to the electric characteristics of the green pixel and a burn-in phenomenon due to a threshold shift of switching occur in the liquid crystal display device of the transverse electric field method. Such a display failure occurs more significantly when PG58 is used for the green pixel, and causes a problem.

Patent document 5 discloses that in a liquid crystal display device of a transverse electric field system, the electric properties of a colored layer as a color filter do not adversely affect the switching performance of liquid crystal, sufficient performance can be ensured without providing a protective layer of a transparent resin, and the colored layer forming a green pixel contains PG36 of a specific amount or less and has a specific dielectric loss tangent (tan δ) value as a color filter capable of coping with high color reproducibility.

However, the technique disclosed in patent document 5 is insufficient in brightness and also insufficient in wide color reproducibility even if a display defect is reduced.

On the other hand, patent document 6 discloses a green composition for a color filter, which contains PG58 and a yellow organic pigment and contains any one selected from a blue pigment, a red pigment, a violet pigment and an orange pigment, as a green composition for a color filter capable of adjusting luminance without lowering high contrast.

However, the technique disclosed in patent document 6 is not sufficient in terms of wide color reproducibility.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-237769

Patent document 2: japanese patent laid-open No. 2012-32767

Patent document 3: japanese patent laid-open publication No. 2013-20558

Patent document 4: japanese patent laid-open No. 2012-108266

Patent document 5: japanese patent laid-open No. 2009-162979

Patent document 6: japanese patent laid-open publication No. 2011-118051

Disclosure of Invention

Problems to be solved by the invention

In recent color filters, various problems in mass production of color filters have to be solved in accordance with a technique for improving color material dispersibility for achieving a demand for higher brightness and higher contrast. That is, in order to increase the color material concentration in the resin composition, it is necessary to increase the dispersant inevitably, and problems such as generation of development residue and delay of development time occur. In addition, if the concentration of the coloring material is increased and the content of the dispersant is increased, the amount of the binder is relatively decreased, and therefore, the colored resin layer is likely to be peeled off from the base substrate during development. Therefore, although high development adhesion is required as a colored resin composition, there is a problem that the level of practical use is not achieved. In addition, in the process of manufacturing a color filter, the colored resin composition once dried is required to have excellent re-solubility in a solvent, that is, excellent re-solubility in a solvent. For example, if a photosensitive colored resin composition adheres to the tip of the die lip when coating is performed by a die coater, a cured product is generated by drying, and if the cured product is not easily dissolved in the photosensitive colored resin composition at the time of resumption of coating, the cured product on the die lip is partially peeled off and easily adheres to the colored layer of the color filter, which causes a foreign matter defect. In particular, when the color material concentration of the colored resin composition is increased, there are problems such as insufficient solvent resolubility, and a decrease in yield due to the generation of the above-mentioned foreign matter in the process of manufacturing the color filter.

However, according to the methods described in patent documents 1 to 2, in addition to the color material dispersibility, all of the problems in mass production of color filters, the generation of development residues, development adhesion, and solvent resolubility are difficult to solve as shown in the comparative examples described below.

In view of the above circumstances, a first object of the present invention is to provide: a color material dispersion liquid which is excellent in color material dispersion stability and can produce a photosensitive coloring resin composition excellent in development adhesion and solvent re-solubility while suppressing the occurrence of development residues; a photosensitive colored resin composition for a color filter, which has excellent dispersion stability of a color material, excellent development adhesion and solvent re-solubility while suppressing the occurrence of development residues, and can form a colored layer having excellent contrast; 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.

In addition, in order to form a green chromaticity region of high color density and to achieve high luminance and high contrast without making the green pixel of the color filter thick, it is desirable to form a green pigment dispersion liquid of bluish green and high luminance, but the green pigment dispersion liquid has not been available in the past.

In view of the above circumstances, a second object of the present invention is to provide: a green color material dispersion liquid exhibiting a bluish green color, having excellent color material dispersion stability and high brightness; a photosensitive colored resin composition for a color filter, which uses the color material dispersion liquid and is excellent in solvent re-solubility, high in brightness and contrast, and capable of forming a colored layer excellent in color reproducibility; a color filter having high brightness, high contrast and excellent color reproducibility using the photosensitive colored resin composition for a color filter; and a liquid crystal display device and an organic light emitting display device having high luminance and excellent color reproducibility by using the color filter.

Means for solving the problems

A color material dispersion liquid for a color filter according to a first aspect of the present invention for solving the first object is a color material dispersion liquid containing a color material, a dispersant, and a solvent; the method is characterized in that:

the dispersant is at least 1 of the following block copolymer (P1) and the following salt-type block copolymer (P2);

p1: a block copolymer having an A block containing a constituent unit represented by the following general formula (I) and a B block containing a constituent unit derived from a carboxyl group-containing monomer;

p2: a salt-type block copolymer in which at least a part of the nitrogen sites at the ends of the constituent units represented by the general formula (I) of the block copolymer and 1 or more compounds selected from the group consisting of compounds represented by the following general formulae (1) to (3) form a salt;

the acid value of the dispersant is 1-18 mgKOH/g, and the glass transition temperature of the dispersant is above 30 ℃;

[ chemical formula 1]

(in the general formula (I), R¹Represents a hydrogen atom or a methyl group, A represents a 2-valent linking group, R²And R³Each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, R²And R³May be bonded to each other to form a ring structure;

in the general formula (1), R^aRepresents a C1-20 linear, branched or cyclic alkyl group, a vinyl group, a phenyl or benzyl group which may have a substituent, or-O-R^e，R^eA linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms; in the general formula (2), R^b、R^b′And R^b″Each independently represents a hydrogen atom, an acidic group or an ester group thereof, an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an optionally substituted vinyl group, an optionally substituted phenyl or benzyl group, or-O-R^f，R^fRepresents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom or an iodine atom; in the general formula (3), R^cAnd R^dAre respectively independentThe structure is represented by a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R^e，R^eA linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms; wherein R is^cAnd R^dContains carbon atoms. )

A color material dispersion liquid for a color filter according to a second aspect of the present invention for solving the second object is a color material dispersion liquid containing a color material, a dispersant, and a solvent; the method is characterized in that:

the color material contains c.i. pigment green 59;

the dispersant is a polymer having a constituent unit represented by the following general formula (I);

[ chemical formula 2]

(in the general formula (I), R¹Represents a hydrogen atom or a methyl group, A represents a 2-valent linking group, R²And R³Each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, R²And R³May be bonded to each other to form a ring structure. )

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

The color filter of the present invention is a color filter comprising at least a transparent substrate and colored layers provided on the transparent substrate, wherein at least one of the colored layers is a colored layer formed by curing the photosensitive colored resin composition for a color filter of the present invention.

The present invention provides a liquid crystal display device having the color filter of the present invention, an opposing substrate, and a liquid crystal layer formed between the color filter and the opposing substrate.

In addition, the present invention provides an organic light emitting display device having the color filter of the present invention described above, and an organic light emitting body.

ADVANTAGEOUS EFFECTS OF INVENTION

According to a first aspect of the present invention, there may be provided: a color material dispersion liquid which is excellent in color material dispersion stability and can produce a photosensitive coloring resin composition excellent in development adhesion and solvent re-solubility while suppressing the occurrence of development residues; a photosensitive colored resin composition for a color filter, which has excellent dispersion stability of a color material, excellent development adhesion and solvent re-solubility while suppressing the occurrence of development residues, and can form a colored layer having excellent contrast; 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.

Further, according to the second aspect of the present invention, there may be provided: a green color material dispersion liquid exhibiting a bluish green color, having excellent color material dispersion stability and high brightness; a photosensitive colored resin composition for a color filter, which uses the color material dispersion liquid and has excellent solvent re-solubility and can form a colored layer with excellent color reproducibility with high brightness and high contrast; a color filter having high brightness, high contrast and excellent color reproducibility using the photosensitive colored resin composition for a color filter; and a liquid crystal display device and an organic light emitting display device having high luminance and excellent color reproducibility by using the color filter.

Drawings

Fig. 1 is a schematic view showing an example of a color filter of the present invention.

Fig. 2 is a schematic diagram 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.

Detailed Description

I. First aspect of the invention

The color material dispersion for a color filter, the photosensitive colored resin composition for a color filter, the liquid crystal display device, and the organic light emitting display device of the present invention will be described in order below.

In the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and further includes radiation including, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves having a wavelength of 5 μm or less, and electron beams.

In the present invention, (meth) acrylic acid represents acrylic acid and methacrylic acid, respectively, and (meth) acrylate represents acrylate and methacrylate, respectively.

In the present specification, the chromaticity coordinates x and y are, without particular limitation, chromaticity coordinates in the XYZ color system of JISZ8701 in which the color is measured using a C light source.

I-1. color material dispersion liquid of first aspect of the present invention

The color material dispersion liquid for a color filter according to the first aspect of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent; the method is characterized in that:

the acid value of the dispersant is 1-18 mgKOH/g, and the glass transition temperature of the dispersant is above 30 ℃.

[ chemical formula 3]

in the general formula (1), R^aRepresents a C1-20 linear, branched or cyclic alkyl group, a vinyl group, a phenyl or benzyl group which may have a substituent, or-O-R^e，R^eA linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms; in the general formula (2), R^b、R^b′And R^b″Each independently represents a hydrogen atom, an acidic group or an ester group thereof, an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an optionally substituted vinyl group, an optionally substituted phenyl or benzyl group, or-O-R^f，R^fRepresents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom or an iodine atom; in the general formula (3), R^cAnd R^dEach independently represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R^e，R^eA linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms; wherein R is^cAnd R^dContains carbon atoms. )

The color material dispersion liquid of the present invention uses at least 1 of the block copolymer (P1) having the specific acid value and the specific glass transition temperature and containing the specific constituent unit and the salt-type block copolymer (P2) in which the block copolymer and the specific compound form a salt as a dispersant, and therefore, a photosensitive colored resin composition having excellent color material dispersion stability, suppressed development residue, and excellent development adhesion and solvent resolubility can be produced. Further, a colored layer having excellent contrast can be formed by using the photosensitive colored resin composition for a color filter prepared from the color material dispersion liquid.

The effects described above are not clarified by using at least 1 kind of the block copolymer (P1) containing the specific constituent unit and having the specific acid value and the specific glass transition temperature and the salt-type block copolymer (P2) in which the block copolymer and the specific compound form a salt as a dispersant, but the following effects are presumed.

It has been known that dispersibility, dispersion stability, and alkali developability can be improved by a block copolymer having an a block containing a specific repeating unit having an amino group or an ammonium salt group and a B block containing a repeating unit having an acidic group as a pigment dispersant (for example,

patent documents

1, 2, and 4).

However, as a result of studies by the present inventors, the method described in patent document 1 has not achieved a practical level of development adhesion in particular. The method described in patent document 1 is presumably because the block copolymer contains a specific repeating unit in which the portion derived from the alcohol of the carboxylic ester contains an alkylene oxide chain, as shown in comparative examples described later, and the glass transition temperature is lowered. When the glass transition temperature of the block copolymer as the pigment dispersant is lower than the temperature of the developer or is close to the temperature, molecular movement of the dispersant during development becomes large, and as a result, it is estimated that development adhesion is lowered.

In addition, the methods described in patent documents 2 and 4 also have not achieved practical levels of development adhesion in particular. In the methods described in patent documents 2 and 4, as shown in comparative examples described later, it is presumed that the reason for this is that the acid value of the dispersant is higher than the value defined in the present application, and therefore, although the developability is excellent, the polarity is excessively high, and peeling is likely to occur. In the methods described in patent documents 2 and 4, it is assumed that the development adhesion does not reach a practical level because there is no idea that the dispersant satisfies both a specific low acid value and a specific high glass transition temperature.

As a result of intensive studies, the present inventors have found that when the acid value of a specific block copolymer or salt-type block copolymer is high, development adhesion does not reach a practical level and solvent resolubility deteriorates; however, a low acid value of a specific value or less has an effect of suppressing development residue, and also can provide good development adhesion with less peeling, and excellent solvent resolubility. On the other hand, it was found that even when the specific block copolymer or salt-type block copolymer had a low acid value of the specific value or less, the development adhesion did not reach a practical level when the glass transition temperature was lower than a predetermined value; when a block copolymer or a salt-type block copolymer having a glass transition temperature higher by 30 ℃ or more than the temperature of the developer is used, the development adhesion is excellent. It is presumed that when a block copolymer or a salt-type block copolymer having a glass transition temperature higher than the temperature of the developer by 30 ℃ or more is used, the molecular movement of the dispersant during development is suppressed, and thus the reduction in development adhesion is suppressed.

The color material dispersion liquid of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range not impairing the effects of the present invention.

The components of the color material dispersion liquid of the present invention are described below in order from the dispersant characteristic to the present invention.

< dispersant >

In the present invention, at least 1 of the block copolymer (P1) and the salt-type block copolymer (P2) is used as the dispersant, wherein the dispersant has an acid value of 1 to 18mgKOH/g, and the dispersant has a glass transition temperature of 30 ℃ or higher.

The constituent unit represented by the general formula (I) contained in the a block has basicity and functions as an adsorption site for the color material. In addition, when at least a part of the nitrogen sites at the end of the constituent unit represented by the general formula (I) forms a salt with 1 or more compounds selected from the group consisting of the general formulae (1) to (3), the salt-forming portion functions as a stronger adsorption site for the color material. On the other hand, the B block containing a constituent unit derived from a carboxyl group-containing monomer functions as a block having solvent-affinity. Therefore, the block copolymer of the present invention shares the functions of the a block adsorbed to the color material and the B block having solvent affinity, and functions as a color material dispersant.

[ Block copolymer ]

{ A Block }

(constituent Unit of the formula (I))

In the general formula (I), A is a direct bond or a 2-valent connecting group. The direct bond means that a does not have an atom, that is, C (carbon atom) and N (nitrogen atom) in the general formula (I) are not bonded via another atom.

Examples of the 2-valent linking group in A include an alkylene group having 1 to 10 carbon atoms, an arylene group, a CONH group, a COO group, an ether group having 1 to 10 carbon atoms (-R '-OR "-: R' and R" are each independently an alkylene group), and combinations thereof.

Among them, A in the general formula (I) is preferably a 2-valent linking group directly bonded to, containing a-CONH-group or a-COO-group, from the viewpoint of dispersibility.

R²And R³In the hydrocarbon group which may contain a hetero atom, examples thereof 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, and a cyclohexyl group, and the number of carbon atoms of the alkyl group is preferably 1 to 18, and more preferably a methyl group or an ethyl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. The number of carbon atoms of the aralkyl group is preferably 7 to 20, more preferably 7 to 14.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12. Among the above-mentioned preferred carbon atoms, the number of carbon atoms not including a substituent is preferably one.

The heteroatom-containing hydrocarbon group has a structure in which a carbon atom in the hydrocarbon group is replaced by a heteroatom. 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.

The hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or the like.

So-called R²And R³Bonded to each other to form a ring structure, means R²And R³A ring structure is formed via the nitrogen atom. R²And R³The ring structure formed may contain heteroatoms. 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, R is preferred²And R³Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R²And R³Bonding to form pyrrolidine ring, piperidine ring, or morpholine ring.

Examples of the constituent unit represented by the above general formula (I) include alkyl-substituted amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate, and alkyl-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide. Among them, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used from the viewpoint of improving dispersibility and dispersion stability.

The constituent unit represented by the general formula (I) may be composed of 1 species, or may contain 2 or more species.

In the a block containing the constituent unit represented by the general formula (I), the constituent unit represented by the general formula (I) preferably contains 3 or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, the content is preferably 3 to 100, more preferably 3 to 50, and still more preferably 3 to 30.

The a block may have a constituent unit other than the constituent unit represented by the general formula (I) within the range in which the object of the present invention is achieved, and may be contained as long as it is a constituent unit copolymerizable with the constituent unit represented by the general formula (I). For example, as the basic block portion can contain structural units other than the structural units represented by the general formula (I), the following B block can be listed as "other structural units", and specific examples thereof include structural units represented by the following general formula (II).

The content ratio of the constituent unit represented by the general formula (I) in the A block in the block copolymer before salt formation is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, most preferably 100% by mass, based on the total mass of all the constituent units of the A block. This is because the higher the proportion of the constituent unit represented by the general formula (I), the higher the adsorption force to the color material, and the better the dispersibility and dispersion stability of the block copolymer. The content ratio of the above-mentioned constituent units is calculated from the packing mass at the time of synthesizing the a block having the constituent unit represented by the general formula (I).

In the block copolymer before salt formation, the content ratio of the constituent unit represented by the general formula (I) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of all the constituent units of the block copolymer, from the viewpoint of satisfactory dispersibility and dispersion stability. The content ratio of each constituent unit in the block copolymer is calculated from the packing quality at the time of synthesizing the block copolymer before salt formation.

The constituent unit represented by the general formula (I) may be 1 type, or may contain 2 or more types, as long as it has affinity with the color material.

{ B Block }

The B block is a block which does not contain the constituent unit represented by the above general formula (I) and contains a constituent unit derived from a carboxyl group-containing monomer. The B block is preferably selected from monomers having an unsaturated double bond copolymerizable with the monomer from which the constituent unit represented by the general formula (I) is derived, and is used as appropriate depending on the solvent so as to have solventropic properties. As a standard, it is preferable to introduce the B block so that the copolymer has a solubility at 23 ℃ of 20 or more (g/100g solvent) relative to the solvent used in combination.

(derived from a carboxyl group-containing monomer)

As the carboxyl group-containing monomer used in the present invention, a monomer having an unsaturated double bond and a carboxyl group which is copolymerizable with a monomer derived from the constituent unit represented by the general formula (I) can be used.

Examples of such monomers include (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic acid anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, or ω -carboxy-polycaprolactone mono (meth) acrylate may also be used. As the precursor of the carboxyl group, an anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride, or the like can be used. Among them, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the constituent unit derived from the carboxyl group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the above-mentioned specific acid value range, and is not particularly limited, but is preferably 0.05 to 4.5% by mass, more preferably 0.07 to 3.7% by mass, based on the total mass of all the constituent units of the block copolymer.

When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is not less than the lower limit, the effect of suppressing the development residue is excellent, and when the content ratio is not more than the upper limit, the deterioration of the development adhesion and the deterioration of the solvent resolubility can be prevented.

The constituent units derived from the carboxyl group-containing monomer may be composed of 1 species or may contain 2 or more species as long as the specific acid value is described above.

(other constituent units)

In the B block, from the viewpoint of making the solvent affinity good, it is general that a constituent unit for improving the solvent affinity may be further contained in addition to a constituent unit derived from the carboxyl group-containing monomer.

The constituent unit constituting the B block includes monomers having an unsaturated double bond copolymerizable with the monomer derived from the constituent unit represented by the general formula (I), and among them, the constituent unit represented by the general formula (II) is preferable.

[ chemical formula 4]

(in the general formula (II), A' is a direct bond or a 2-valent linking group, R⁴Represents a hydrogen atom or a methyl group, R⁵Represents a hydrocarbon group, - [ CH (R)⁶)-CH(R⁷)-O]_x-R⁸Or- [ (CH)₂)_y-O]_z-R⁸The 1-valent radical shown. R⁶And R⁷Each independently is a hydrogen atom or a methyl group, R⁸Is a hydrogen atom, a hydrocarbyl radical, -CHO, -CH₂CHO or-CH₂COOR⁹A 1-valent radical shown, R⁹Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The above 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' may be the same as A in the general formula (I). Among these, from the viewpoint of solubility in organic solvents, a 2-valent linking group containing a-CONH-group or-COO-group, which is directly bonded, is preferable.

In the general formula (II), R⁵Represents a hydrocarbon group, - [ CH (R)⁶)-CH(R⁷)-O]_x-R⁸Or- [ (CH)₂)_y-O]_z-R⁸。

As R⁵The hydrocarbon group in (1) 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 examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl, bornyl, isobornyl, dicyclopentyl, dicyclopentenyl, adamantyl and lower alkyl-substituted adamantyl.

The alkenyl group having 2 to 18 carbon atoms may be any of straight-chain, branched, and cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl. The position of the double bond of the alkenyl group is not limited, and it is preferable to have a double bond at the terminal of the alkenyl group from the viewpoint of reactivity of the obtained polymer.

Examples of the substituent of the aliphatic hydrocarbon group 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, and a xylyl group, and the aryl group may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 to 24, more preferably 6 to 12.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent. The number of carbon atoms of the aralkyl group is preferably 7 to 20, more preferably 7 to 14.

Examples of the substituent of the aromatic ring such as aryl or aralkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, and a halogen atom.

The above-mentioned number of carbon atoms preferably does not include the number of carbon atoms of the substituent.

R is as defined above⁵Wherein x is an integer of 1 to 18, preferably an integer of 1 to 4, and more preferably an integer of 1 to 2; y is an integer of 1 to 5, preferably an integer of 1 to 4, and more preferably 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.

R is as defined above⁸The hydrocarbon group in (1) may be the same as R⁵The same is shown.

R⁹The alkyl group is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be linear, branched or cyclic.

R in the constituent unit represented by the above general formula (II)⁵And may be the same as or different from each other.

As the above-mentioned R⁵Among them, those having excellent compatibility with a solvent described later are preferably selected, and specifically, for example, those used in the solvent are preferably selected as color filtersIn the case of a glycol ether acetate, ether, ester or other solvent generally used as a solvent for the colored resin composition for a sheet, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl or the like is preferable.

Further, the above-mentioned R⁵The substituent may be a group substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, or an isocyanate group, as long as the dispersibility of the block copolymer is not impaired, or the substituent may be added by reacting the block copolymer with a compound having the substituent after the synthesis of the block copolymer.

The number of the constituent units constituting the B block is not particularly limited, and is preferably 10 to 300, more preferably 10 to 100, and still more preferably 10 to 70, from the viewpoint of effectively functioning the solvent-philic site and the color material site and improving the dispersibility of the color material.

The content ratio of the constituent unit represented by the general formula (II) in the B block in the block copolymer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on the total mass of all the constituent units of the B block, from the viewpoint of improving the solvent-affinity or the color material dispersibility. The content ratio of the above-mentioned constituent units is calculated from the packing mass at the time of synthesizing the B block having the constituent unit derived from the carboxyl group-containing monomer.

In the block copolymer before salt formation, the content ratio of the constituent unit represented by the above general formula (II) is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total mass of all the constituent units of the block copolymer, from the viewpoint of improving dispersibility of the color material. The content ratio of the above-mentioned constituent units is calculated from the packing quality at the time of synthesizing the block copolymer before salt formation.

The B block may be constituted of 1 type of the constituent unit represented by the above general formula (II), or may contain 2 or more types of the constituent units, as long as the constituent units are appropriately selected so as to function as a solvent-philic portion. The 2 or more kinds of constituent units contained in the B block may be arranged randomly in the block.

In the present invention, the B block of the block copolymer preferably contains a constituent unit derived from a hydroxyl group-containing monomer from the viewpoint of improving development adhesion. It is considered that when the hydroxyl group-containing monomer contains a constituent unit derived from the hydroxyl group-containing monomer, the monomer easily interacts with glass, metal, or the like which is generally used as a substrate, and therefore, development adhesion is improved. When the block B contains a constituent unit derived from a hydroxyl group-containing monomer, the development speed is further improved.

Here, the hydroxyl group means an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As the constituent unit derived from the hydroxyl group-containing monomer, a monomer having an unsaturated double bond and a hydroxyl group which is copolymerizable with the monomer derived from the constituent unit represented by the general formula (I) can be used. Examples of such monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, an epsilon-caprolactone 1-mole adduct of 2-hydroxyethyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

From the viewpoint of improving developability, a hydroxyl group having a 1-order hydroxyl group is more preferable than a hydroxyl group having a 2-order hydroxyl group. The "1-order hydroxyl group" means a hydroxyl group having 1-order carbon atom as the carbon atom to which the hydroxyl group is bonded; the 2-membered hydroxyl group means a hydroxyl group having a carbon atom to which the hydroxyl group is bonded as a 2-membered carbon atom.

As described later, from the viewpoint of improving development adhesion, the dispersant used in the present invention preferably uses a hydroxyl group-containing monomer having a homopolymer of each monomer and a glass transition temperature (Tgi) of 0 ℃ or higher, and more preferably a hydroxyl group-containing monomer having a glass transition temperature of 10 ℃ or higher.

From the viewpoint of improving the development adhesion, among them, 1 or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate is preferable.

In the block copolymer (P1) before salt formation, the content of the constituent unit derived from the hydroxyl group-containing monomer is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more, based on the total mass of all the constituent units of the block copolymer. When the amount is not less than the lower limit, the resultant composition can exhibit preferable development adhesion. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. When the content is not more than the above upper limit, a preferable product can be obtained from the viewpoint of increasing the introduction ratio of other useful monomers. The content ratio of the above-mentioned constituent unit is calculated from the packing quality at the time of synthesizing the block copolymer before salt formation.

In the present invention, the B block preferably contains a constituent unit derived from an aromatic group-containing monomer from the viewpoint of improving the solvent re-solubility. It is considered that when the monomer contains a constituent unit derived from an aromatic group-containing monomer, the compatibility with a solvent or other components is easily improved, and the solvent re-solubility is improved.

As the constituent 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 derived from the constituent unit represented by the general formula (I) can be used. Examples of such monomers include acrylic esters such as benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrenes such as styrene, and vinyl ethers such as phenyl vinyl ether.

As described later, the dispersant used in the present invention has a glass transition temperature of a specific value or higher, and from the viewpoint of improving development adhesion, among them, an aromatic group-containing monomer having a homopolymer of each monomer with a glass transition temperature (Tgi) of 0 ℃ or higher is preferably used, and an aromatic group-containing monomer having a glass transition temperature (Tgi) of 10 ℃ or higher is more preferably used.

Among them, from the viewpoint of easy improvement of the re-solubility, 1 or more selected from the group consisting of benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and phenoxyethyl (meth) acrylate is preferable, and 1 or more selected from the group consisting of benzyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate is more preferable.

In addition, the content ratio of the constituent unit derived from the aromatic group-containing monomer in the block copolymer (P1) before salt formation is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more, relative to the total mass of all the constituent units of the block copolymer, from the viewpoint of improving the solvent re-solubility. When the lower limit value is not less than the above lower limit value, a preferable solvent re-solubility can be obtained. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. When the content is not more than the above upper limit, a preferable product can be obtained from the viewpoint of increasing the introduction ratio of other useful monomers.

Among them, the B block having a solventropic property preferably contains (i) a constituent unit derived from a hydroxyl group-containing monomer and a constituent unit derived from an aromatic group-containing monomer, from the viewpoint of improving development adhesion and solvent re-solubility; and (ii) at least 1 kind of constituent unit derived from a carboxyl group-and aromatic group-containing monomer.

When (i) the constituent unit derived from the hydroxyl group-containing monomer and (ii) the constituent unit derived from the aromatic group-containing monomer are contained, the constituent unit derived from the hydroxyl group-containing monomer is contained in an amount of preferably 0.15 parts by mass or more, more preferably 0.5 parts by mass or more, based on 1 part by mass of the constituent unit derived from the aromatic group-containing monomer. When the lower limit value is not less than the above lower limit value, a product having excellent development adhesion can be obtained. Similarly, the hydroxyl group-containing monomer-derived constituent unit is preferably contained in an amount of 15 parts by mass or less, more preferably 7 parts by mass or less, based on 1 part by mass of the aromatic group-containing monomer-derived constituent unit. This is because, if the amount is less than the above upper limit, a product having excellent solvent re-solubility can be obtained. Among these, it is particularly preferable that the hydroxyl group-containing monomer-derived constituent unit having a glass transition temperature value (Tgi) of the homopolymer of 10 ℃ or higher is contained in the above range with respect to 1 part by mass of the aromatic group-containing monomer-derived constituent unit having a glass transition temperature value (Tgi) of 10 ℃ or higher of the homopolymer. By containing the components at the lower limit or more, a product having more excellent development adhesion can be obtained, and by containing the components at the upper limit or less, a product having more excellent solvent solubility can be obtained.

Examples of (ii) the monomer having a hydroxyl group and an aromatic group in the constituent unit derived from the hydroxyl group-and aromatic group-containing monomer include 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid. The homopolymer of 2-hydroxy-3-phenoxypropyl (meth) acrylate has a glass transition temperature value (Tgi) of 10 ℃ or higher, and is preferably used from the viewpoint that either the effect obtained from the constituent unit derived from the hydroxyl group-containing monomer or the effect obtained from the constituent unit derived from the aromatic group-containing monomer can be obtained. That is, it is preferable from the viewpoint of improving development adhesion, development speed, and solvent resolubility.

(ii) When the monomer contains a structural unit derived from a hydroxyl group-and aromatic group-containing monomer, since the development adhesion, development speed, and solvent resolubility can be improved by 1 structural unit, there is also an advantage that the introduction ratio of other functional monomers can be increased.

As described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving development adhesion, it is preferable that the total content of the monomers having a value of the glass transition temperature of a homopolymer of the monomers (Tgi) of 10 ℃ or more in the B block is set to 75% by mass or more, and more preferably 85% by mass or more.

In the block copolymer (P1), the ratio m/n of the number m of units constituting the a block to the number n of units constituting the B block is preferably in the range of 0.05 to 1.5, and more preferably in the range of 0.1 to 1.0 from the viewpoint of dispersibility and dispersion stability of the color material.

The amine value of the block copolymer (P1) before salt formation is not particularly limited, but from the viewpoint of color material dispersibility and dispersion stability, the lower limit is preferably 40mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 60mgKOH/g or more. The upper limit is preferably 140mgKOH/g or less, more preferably 130mgKOH/g or less, and still more preferably 120mgKOH/g or less. When the amount is not less than the lower limit, the dispersion stability is further excellent. When the content is not more than the upper limit, the compatibility with other components is excellent and the solvent re-solubility is good.

In the present invention, the amine value of the block copolymer before salt formation means the mass (mg) of potassium hydroxide equivalent to 1g of hydrochloric acid required for neutralizing the solid content of the block copolymer before salt formation, and is a value measured according to the method described in JIS K7237.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, more preferably 2000 to 15000, and still more preferably 3000 to 12000, from the viewpoint of improving the dispersibility and dispersion stability of the color material.

Here, the weight average molecular weight (Mw) was determined as a standard polystyrene equivalent by Gel Permeation Chromatography (GPC).

In the present invention, the weight average molecular weight Mw of the block copolymer is determined by GPC (gel permeation chromatography) as a standard polystyrene equivalent. Measurement was carried out using HLC-8120GPC manufactured by Tosoh corporation, N-methylpyrrolidone to which 0.01 mol/l of lithium bromide was added as an elution solvent, Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, and 580 (above, Easi PS-2 series manufactured by Polymer laboratories, Inc.) and Mw1090000 (manufactured by Tosoh corporation) as calibration curves based on polystyrene standards, and TSK-GEL ALPHA-MX2 (manufactured by Tosoh corporation) as a measurement column. The macromonomer, salt type block copolymer, and graft copolymer which are the raw materials of the block copolymer are also performed under the above-mentioned conditions.

In the present invention, the arrangement of the blocks of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, an AB block copolymer or an ABA block copolymer is preferable from the viewpoint of excellent dispersibility.

The method for producing the block copolymer is not particularly limited, and the block copolymer can be produced by a known method, and among them, the block copolymer can be produced preferably by a living polymerization method. This is because the chain rotation or deactivation is less likely to occur, a copolymer having a uniform molecular weight can be produced, and the dispersibility can be improved. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization and group transfer polymerization, and living cationic polymerization methods. By sequentially polymerizing the monomers by these methods, a copolymer can be produced. For example, a block copolymer can be produced by first producing an a block and then polymerizing the constituent units constituting the B block on the a block. In the above production method, the polymerization order of the a block and the B block may be reversed. Alternatively, the A block and the B block can be separately prepared and then coupled.

[ salt type block copolymer ]

In the present invention, a salt-type block copolymer in which at least a part of the nitrogen sites at the end of the constituent unit represented by the above general formula (I) of the block copolymer and 1 or more compounds selected from the group consisting of the compounds represented by the above general formulae (1) to (3) form a salt can be used.

The salt-forming site in the constituent unit represented by the general formula (I) is preferably used from the viewpoint of further improving the adsorption property of a color material and improving the dispersibility of a color material.

(1 or more compounds selected from the group consisting of the compounds represented by the above general formulae (1) to (3))

In the above general formulae (1) to (3), R is^a、R^b、R^b′、R^b″、R^c、R^d、R^eAnd R^fThe linear, branched or cyclic alkyl group having 1 to 20 carbon atoms in (b) may be either a linear or branched one or may have a cyclic structure, and specifically, it includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and the likeAlkyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, dodecyl, cyclopentyl, cyclohexyl, tetradecyl, octadecyl, and the like. The alkyl group may preferably be a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and more preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.

In addition, R^a、R^c、R^dAnd R^eAmong them, examples of the substituent of the phenyl group or the benzyl group which may have a substituent include an alkyl group having 1 to 5 carbon atoms, an acyl group, an acyloxy group and the like.

R^b、R^b′、R^b″And R^fExamples of the substituent of the phenyl group or benzyl group which may have a substituent include an acidic group or an ester group thereof, an alkyl group having 1 to 5 carbon atoms, an acyl group, and an acyloxy group.

In addition, R^b、R^b′、R^b″And R^fIn the above formula, examples of the substituent of the linear, branched or cyclic alkyl group or vinyl group having 1 to 20 carbon atoms, which may have a substituent, include an acidic group or an ester group thereof, a phenyl group, an acyl group, an acyloxy group and the like.

R^b、R^b′、R^b″And R^fThe acidic group in (1) refers to a group which releases a proton in water to exhibit acidity. Specific examples of the acidic group include a carboxyl group (-COOH) and a sulfonic acid group (-SO)₃H) Phosphate (-O) (OH)₂) Phospho-subunit (> P (═ O) (OH)), boronic acid group (-b (OH))₂) And a boronic acid group (& gt, BOH), etc., may be an anion in which a hydrogen atom is dissociated such as a carboxylate group (-COO-), etc., or may be an acidic salt forming a salt with an alkali metal ion such as a sodium ion or a potassium ion.

Examples of the ester group of the acidic group include a carboxylate group (-COOR) and a sulfonate group (-SO)₃R), phosphate (-P (═ O) (OR)₂) Phosphate subunit (> P (═ O) (OR)), borate group (-B (OR))₂) Boronate subunit (> BOR), and the like. Among them, the ester group as the acidic group is preferably a carboxylic acid ester group (-COOR) from the viewpoint of dispersibility and dispersion stability. Need to make sure thatR is a hydrocarbon group, is not particularly limited, and is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group, from the viewpoint of dispersibility and dispersion stability.

The compound of the general formula (2) preferably has 1 or more functional groups selected from the group consisting of a carboxyl group, a boronic acid subunit, anions thereof, alkali metal salts thereof, and esters thereof from the viewpoint of dispersibility, dispersion stability, alkali developability, and suppression of development residue, and more preferably has a functional group selected from the group consisting of a carboxyl group, a carboxylate group, and a carboxylate group.

When the compound of the general formula (2) has an acidic group or an ester group thereof (hereinafter referred to as an acidic group or the like), it is presumed that any of the hydrocarbons on the acidic group side or the like and the halogen atom side of the compound can form a salt with the terminal nitrogen site, and 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 forms a salt with the acidic group or the like. Further, it is presumed that the dispersibility and dispersion stability can be improved by adsorbing the color material at the stably existing salt-forming site.

When the compound of the general formula (2) has the above acidic group or the like, it may have 2 or more of the above acidic group or the like. When 2 or more of the above acidic groups or the like are present, a plurality of the above acidic groups or 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 still more preferably 1.

R in the above general formula (1)^aR in the above general formula (2)^b、R^b′And R^b″And R in the above general formula (3)^cAnd R^dWhen at least one of the above groups has an aromatic ring, the affinity with the skeleton of the coloring material described later can be improved, and the coloring composition is excellent in dispersibility and dispersion stability of the coloring material, and is preferable from the viewpoint of obtaining a coloring composition excellent in contrast.

The molecular weight of 1 or more compounds selected from the group consisting of the above general formulae (1) to (3) is preferably 1000 or less, more preferably 50 to 800, still more preferably 50 to 400, yet more preferably 80 to 350, and most preferably 100 to 330, from the viewpoint of improving the dispersibility of the color material.

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, and a hydrate such as p-toluenesulfonic acid monohydrate is 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 bromide, benzyl iodide, chlorobenzene, α -chlorophenylacetic acid, α -bromophenylacetic acid, α -iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-iodophenylbenzoic acid, chloroacetic acid, bromoacetic acid, iodoacetic acid, α -bromophenylacetic acid methyl ester, and 3- (bromomethyl) phenylboronic acid, and examples of the compound represented by the general formula (3) include monobutylphosphoric acid, dibutylphosphoric acid, methylphosphoric acid, dibenzylphosphoric acid, diphenylphosphoric acid, phenylpropylphosphinic acid, and acid ethylphosphoric acid.

From the viewpoint of particularly excellent dispersion stability, 1 or more selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethylacryloxyethyl acid phosphoric acid, dibutyl phosphoric acid, benzyl chloride, benzyl bromide, vinylsulfonic acid, and p-toluenesulfonic acid monohydrate is preferable, and among these, 1 or more selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, benzyl bromide, and p-toluenesulfonic acid monohydrate is preferably used.

In addition, from the viewpoint of excellent dispersion stability and an improvement in the effect of suppressing development residue by combining with a block copolymer (P1) having an acid value, it is also preferable to use a compound represented by the general formula (2) having an acid group and an ester group thereof, and among them, 1 or more selected from the group consisting of α -chlorophenylacetic acid, α -bromophenylacetic acid, α -iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid is also preferable.

In the salt-type block copolymer, the content of 1 or more compounds selected from the group consisting of the above-described general formulae (1) to (3) forms a salt with the nitrogen site at the end of the constituent unit represented by the general formula (I), and therefore 1 or more compounds selected from the group consisting of the above-described general formulae (1) to (3) are contained in an amount of 0.01 mole or more, more preferably 0.1 mole or more, still more preferably 0.2 mole or more, and particularly preferably 0.3 mole or more, based on 1 mole of the nitrogen site at the end of the constituent unit represented by the general formula (I). When the amount is not less than the above lower limit, the effect of improving the dispersibility of the color material due to salt formation can be easily obtained. Similarly, the amount is preferably 1mol or less, more preferably 0.8 mol or less, still more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When the content is not more than the above upper limit, a product having excellent development adhesion and solvent re-solubility can be obtained.

The 1 or more compounds selected from the group consisting of the above general formulae (1) to (3) may be used alone in 1 kind, or 2 or more compounds may be used in combination. When 2 or more kinds are combined, the total content is preferably within the above range.

The method for preparing the salt-type block copolymer includes a method of adding 1 or more compounds selected from the group consisting of the above general formulae (1) to (3) to a solvent in which the above block copolymer is dissolved or dispersed, stirring the mixture, and heating the mixture as necessary.

The nitrogen site at the end of the structural unit represented by the general formula (I) of the block copolymer and the 1 or more compounds selected from the group consisting of the above general formulae (1) to (3) form 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 (P2) was smaller than that of the block copolymer (P1) before salt formation, in which only the salt was formed. However, since the salt-forming site is the same as or stronger than the nitrogen site at the end corresponding to the amino group, the dispersibility of the color material or the dispersion stability of the color material tends to be improved by salt formation. In addition, the salt-forming site, like the amino group, if too much, adversely affects the solvent re-solubility. Therefore, in the present invention, the amine value of the block copolymer (P1) before the salt formation can be used as an index for improving the dispersion stability of the color material and the solvent re-solubility. The amine value of the salt-type block copolymer (P2) is preferably 0 to 130mgKOH/g, more preferably 0 to 120 mgKOH/g.

When the content is not more than the above upper limit, the compatibility with other components is excellent and the solvent re-solubility is good.

In the salt-type block copolymer (P2), the amine value of the salt-type block copolymer in which a salt is formed by the compound represented by the above general formula (2) can be a value measured according to the method described in JIS K7237. In the compound of the general formula (2), since the nitrogen site at the end of the constituent unit represented by the general formula (I) forms a salt with the hydrocarbon on the halogen atom side, the salt formation state is not changed even by this measurement method, and thus the amine value can be measured.

On the other hand, in the salt-type block copolymer (P2), the amine value of the salt-type block copolymer in which a salt is formed using the compound represented by the above general formula (1) or (3) is calculated from the amine value of the block copolymer before the salt formation as described below. In the compound represented by the above general formula (1) or (3), since the nitrogen site at the end of the structural unit represented by the general formula (I) forms a salt with an acidic group, when the amine value of such a salt-type block copolymer is measured by the method described in JIS K7237, the state of the salt formation changes, and thus an accurate value cannot be measured.

First, the amine value of the block copolymer (P1) before salt formation was determined by the above method. Then, 13C-NMR spectra of the salt-type block copolymer were measured using a nuclear magnetic resonance apparatus, and the obtained spectrum data was analyzed for the reactivity (ratio of nitrogen site at salt-forming end) of 1 or more compounds selected from the group consisting of the above-mentioned general formula (1) and (3) with respect to the nitrogen site at end of the structural unit represented by the above-mentioned general formula (I) in the nitrogen site at end of the structural unit represented by the above-mentioned general formula (I) by using the ratio of integrated values of the carbon atom peak adjacent to the nitrogen atom not forming a salt and the carbon atom peak adjacent to the nitrogen atom forming a salt. The amine value of the nitrogen site at the end of the constitutional unit represented by general formula (I) after salification of 1 or more compounds selected from the group consisting of general formula (1) or (3) is 0, and the amine value consumed for salt formation calculated from (amine value of block copolymer before salt formation (P1) measured by the method described in JIS K7237) × (nitrogen site ratio (%) at the end of formed salt calculated from 13C-NMR spectrum/100) is determined by subtracting the amine value consumed for salt formation from the amine value of the block copolymer before salt formation.

The amine value of the salt-type block copolymer (P2) ({ the amine value of the block copolymer before salt formation (P1) measured by the method described in JIS K7237 } - { the amine value of the block copolymer before salt formation (P1) measured by the method described in JIS K7237 } × { the nitrogen site ratio at the end of the formed salt (%)/100 } calculated by 13C-NMR spectroscopy

The acid value of the dispersant used in the present invention is set to a lower limit of 1mgKOH/g or more from the viewpoint of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2mgKOH/g or more from the viewpoint of more excellent effect of suppressing development residue. The upper limit of the acid value of the dispersant used in the present invention is 18mgKOH/g or less from the viewpoint of preventing deterioration of development adhesion and solvent resolubility. Among these, the acid value of the dispersant is more preferably 16mgKOH/g or less, and still more preferably 14mgKOH/g or less, from the viewpoint of satisfactory development adhesion and solvent re-solubility.

In the dispersant used in the present invention, the acid value of the block copolymer (P1) before salt formation is preferably 1mgKOH/g or more, more preferably 2mgKOH/g or more. This is because the effect of suppressing the development residue can be improved. The upper limit of the acid value of the block copolymer (P1) before salt formation is 18mgKOH/g or less, preferably 16mgKOH/g or less, and more preferably 14mgKOH/g or less. This is to improve the development adhesion and solvent re-solubility.

As described above, the acid value of the block copolymer (P1) before salt formation represents the mass (mg) of potassium hydroxide required for neutralizing the acidic components contained in 1g of the solid content of the block copolymer, and is a value measured according to the method described in JIS K0070.

The acid value of the salt block copolymer (P2) in which a salt is formed from the compound represented by the above general formula (2) is also a value measured by the method described in JIS K0070. The compound of the general formula (2) can be measured without changing the state of salt formation even by this measurement method because the nitrogen site at the end of the constituent unit represented by the general formula (I) forms a salt with the hydrocarbon on the halogen atom side.

On the other hand, in the case of the salt block copolymer in which the salt is formed from the salt block copolymer (P2) using the compound represented by the above general formula (1) or (3), the acid value is calculated by removing the acidic group used for salt formation. This is because the acidic group used for the salt formation does not function as an acidic group for increasing the acid value of the dispersant. Therefore, in the present application, the acid value of the salt-type block copolymer in which a salt is formed by using the compound represented by the above general formula (1) or (3) is calculated from the value obtained by the following formula. This is because, when the acid value of the salt-type block copolymer in which a salt is formed from the compound represented by the above general formula (1) or (3) is measured by the method described in JIS K0070, the state of the salt formation is changed, and a correct value cannot be measured.

The acid value of the salt-type block copolymer (P2) { the total acid value of the compound represented by the above general formula (1) or (3) used for salt formation-the acid value consumed for salt formation } + the acid value of the block copolymer (P1) before salt formation } + the acid value of the block copolymer (P1)

The total acid value of the compound represented by the general formula (1) or (3) used for the salt formation can be measured by the method described in JISK 0070. On the other hand, the acid value consumed for salt formation was calculated from the salt formation ratio obtained by NMR.

Specifically, the acid value consumed for salt formation is measured, for example, by a nuclear magnetic resonance apparatus from 13C-NMR spectrum of the salt-type block copolymer, and the ratio of the number of nitrogen atoms at the end of the salt formation to the total number of nitrogen sites at the end is calculated from the ratio of the integrated values of the peaks of carbon atoms adjacent to the nitrogen atom not forming the salt and the peaks of carbon atoms adjacent to the nitrogen atom forming the salt in the obtained spectral data. The consumed amine value was calculated from { amine value of the block copolymer (P1) before salt formation (P1) measured by the method described in JIS K7237) × { nitrogen site ratio (%) at the end of the formed salt calculated from 13C-NMR spectrum/100 }, and the value was the same as the acid value consumed for salt formation.

However, when the compound represented by the above general formula (1) is caused to form a salt in an amount of 1mol or less, the compound represented by the above general formula (3) having 1 acidic group is caused to form a salt in an amount of 1mol or less, or the compound represented by the above general formula (3) having 2 acidic groups is caused to form a salt in an amount of 0.5 mol or less, based on 1mol of the terminal nitrogen site of the constituent unit represented by the general formula (I), the total amount of the acidic groups and the terminal nitrogen site of the constituent unit represented by the general formula (I) form a salt, and the acidic groups do not affect the acid value in the salt-type block copolymer after salt formation, and therefore, the acid value can be set to be the same as that in the block copolymer before salt formation.

On the other hand, in the case where the compound represented by the above general formula (3) having 2 acidic groups is added in a molar amount exceeding the above, since an acidic group which does not form a salt is present in the dispersant after salt formation, the acid value of the dispersant is calculated by adding the acid value of the part of the acidic group which does not form a salt to the acid value of the block copolymer before salt formation as described above.

In the present invention, the glass transition temperature of the dispersant is 30 ℃ or higher. That is, the glass transition temperature of the dispersant is 30 ℃ or higher regardless of whether it is a block copolymer (P1) or a salt-type block copolymer (P2).

When the glass transition temperature of the dispersant is lower than 30 ℃, particularly equal to or lower than the temperature of the developer (usually about 23 ℃), the development adhesion is reduced. This is presumably because: when the glass transition temperature is equal to or lower than or close to the temperature of the developer, 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 32 ℃ or higher, more preferably 35 ℃ or higher, from the viewpoint of development adhesion. On the other hand, from the viewpoint of ease of handling in use such as accurate weighing, it is preferably 200 ℃ or lower.

The glass transition temperature of the dispersant in the present invention is determined by Differential Scanning Calorimetry (DSC) based on JIS K7121.

The glass transition temperature (Tg) of the block copolymer not forming a salt is calculated by the following formula and is used as an index.

1/Tg＝∑(Xi×Tgi)

Here, the block copolymer is obtained by copolymerizing n monomer components from 1 to n. Xi is the weight fraction of the ith monomer (Σ Xi ═ 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the ith monomer. Where Σ is the sum of i and 1 to n. It should be noted that the glass transition temperature (Tgi) of the homopolymer of each monomer can be determined by the value of Polymer Handbook, 3rd Edition (j. brand, e.h. immergut, Wiley-Interscience, 1989).

The glass transition temperature obtained from the calculated value is almost the same as the measured value obtained by DSC, as shown in examples described later, and therefore, it can be used as an index of the glass transition temperature of a block copolymer in which no salt is formed.

In the color material dispersion liquid of the present invention, at least 1 of the block copolymer and the salt-type block copolymer is used as the dispersant, and the content thereof is appropriately selected depending on the kind of the color material to be used, the solid content concentration in the photosensitive colored resin composition for a color filter to be described later, and the like.

The content of the dispersant is preferably 3 to 45 parts by mass, more preferably 5 to 35 parts by mass, per 100 parts by mass of the total solid content in the color material dispersion liquid. When the lower limit value is not less than the above lower limit value, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive colored resin composition for a color filter is further excellent. When the amount is not more than the upper limit, the developability is good.

Particularly, when a coating film or a colored layer having a high color material concentration is formed, the content of the dispersant is preferably 3 to 25 parts by mass, more preferably 5 to 20 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion.

In the present invention, the solid component is not limited to the above-mentioned solvent, and includes a monomer dissolved in a solvent.

< color Material >

In the present invention, the color material is not particularly limited as long as it can emit a desired color when forming a colored layer of the color filter, and various organic pigments, inorganic pigments, and dispersible dyes can be used alone or in combination of 2 or more. Among them, organic pigments are preferably used because they have high color-developing properties and high heat resistance. Examples of the organic Pigment include compounds classified as pigments (Pigment) in the color index (C.I.; issued by the society of Dyers and Colourists Co., Ltd.), and specifically, pigments having a color index (C.I.) number attached thereto as described below.

Derivative pigments of 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, 185, and c.i. pigment yellow 150;

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, 57:1, 57:2, 58:4, 60:1, 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, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 255, 202, 209, 215, 220, 265;

c.i. pigment blue 15, 15:3, 15:4, 15:6, 60;

c.i. pigment green 7, 36, 58, 59;

c.i. pigment brown 23, 25;

c.i. pigment black 1, 7.

Among these, the c.i. pigment green 59 is preferably contained as the color material from the viewpoint of obtaining a green color material dispersion liquid exhibiting bluish green color, excellent in color material dispersion stability, and high in luminance. When the green color material dispersion is used, the green pixel of the color filter can be formed into a green chromaticity region having a high color density without increasing the thickness of the green pixel, and high luminance and high contrast can be realized. The c.i. pigment green 59 will be described in detail in the description of the second aspect of the present invention described later. The derivative pigment of c.i. pigment yellow 150 is also described in detail in the following description of the second aspect of the present invention.

Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead yellow, zinc yellow, indian red (Bengala, red iron (III) oxide), cadmium red, ultramarine, berlin blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

For example, when a light-shielding layer pattern is formed on a substrate of a color filter by using the color material dispersion of the present invention as a photosensitive colored resin composition for a color filter, which will be described later, a black pigment having high light-shielding properties is blended in the ink. As the black pigment having high light-shielding properties, for example, an inorganic pigment such as carbon black or ferroferric oxide, or an organic pigment such as cyanine black can be used.

Examples of the dispersible dye include dyes that are rendered dispersible by adding various substituents to the dye, by insolubilizing the dye in a solvent by a known lake (salt formation) method, or by using a solvent having low solubility in combination. By using such a dispersible dye in combination with the above-mentioned dispersant, the dispersibility and dispersion stability of the dye can be improved.

As the dispersible dye, one can be appropriately selected from existing dyes. Examples of such dyes include azo dyes, metal double salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.

As a standard, when the amount of the dye dissolved is 10mg or less relative to 10g of the solvent (or the mixed solvent), it can be judged that the dye is dispersible in the solvent (or the mixed solvent).

The average primary particle size of the color material used in the present invention is not particularly limited as long as it can emit a desired color when the color layer of the color filter is formed, and varies depending on the type of the color material used, but is preferably within a range of 10 to 100nm, and more preferably 15 to 60 nm. When the average primary particle size of the color material is in the above range, a display device including a color filter manufactured using the color material dispersion liquid of the present invention can have a high contrast and a high quality.

The average primary particle diameter of the color material of the present invention is represented by "volume distribution median particle diameter (D50)". In a field emission scanning electron microscope (S-4800) manufactured by hitachi High Technologies, a dedicated bright field STEM mount and a selective detector were installed so that the microscope could be used as a scanning transmission electron microscope (hereinafter, abbreviated as "STEM"), and a 20-ten-thousand-fold STEM photograph was taken, and inputted into the following software, 100 color materials were arbitrarily selected on the photograph, and the diameters (span lengths) thereof were measured, and the average primary particle size of the color materials was determined from the volume-based distribution as a 50% cumulative particle size in terms of volume.

The color material and toluene were mixed, and the mixture was dropped onto a collodion film-attached web to prepare a sample for STEM measurement. When the volume-based particle size distribution or the volume distribution median particle size (D50) was obtained from the STEM photograph, image analysis type particle size distribution measurement software "Mac-View ver.4" manufactured by Mountech corporation was 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 within a range of 10 to 100nm, more preferably within a range of 15 to 60 nm.

The average dispersed particle diameter of the color material in the color material dispersion liquid is the dispersed particle diameter of the color material particles dispersed in the dispersion medium containing at least the solvent, and is measured by a laser scattering particle size distribution meter. The particle size measurement by the laser scattering particle size distribution meter may be performed by a dynamic light scattering method at 23 ℃ using a laser scattering particle size distribution meter (for example, NANOTRACK particle size distribution measuring apparatus UPA-EX150 manufactured by NIGHTRO CORPORATION), while appropriately diluting the color material dispersion with a solvent used in the color material dispersion to a concentration (for example, 1000 times or the like) that can be measured by the laser scattering particle size distribution meter. The average distribution particle diameter herein is a volume average particle diameter.

The color material used in the present invention can be produced by a known method such as recrystallization and solvent salt milling. Further, commercially available color materials may be used by 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. The content of the color material is preferably 5 to 80 parts by mass, more preferably 8 to 70 parts by mass, per 100 parts by mass of the total solid content in the color material dispersion liquid, from the viewpoint of dispersibility and dispersion stability.

Particularly, when a coating film or a colored layer having a high color material concentration is formed, the amount is preferably 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion.

< solvent >

The solvent used in the present invention is not particularly limited as long as it is an organic solvent which does not react with each component in the color material dispersion liquid and can dissolve or disperse them. The solvents may be used singly or in combination of 2 or more.

Specific examples of the solvent include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methyl alcohol, and ethyl alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; carbitol acetate-based solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and Butyl Carbitol Acetate (BCA); diacetates such as propylene glycol diacetate and 1, 3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ -butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; and aromatic hydrocarbons such as toluene and xylene. Of these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, from the viewpoint of solubility of other components and coating suitability, the solvent used in the present invention is preferably 1 or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Butyl Carbitol Acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate.

The color material dispersion liquid of the present invention contains the solvent in an amount of usually preferably 55 to 95% by mass, more preferably 65 to 90% by mass, and still more preferably 70 to 88% by mass, based on the total amount of the color material dispersion liquid containing the solvent. If the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. In addition, if the solvent is too much, the color material concentration decreases, and it is difficult to achieve the target chromaticity coordinates.

< other ingredients >

In the color material dispersion liquid of the present invention, a dispersion auxiliary resin and other components may be further blended as necessary without impairing the effects of the present invention.

Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by photosensitive colored resin compositions for color filters described later. The steric hindrance of the alkali-soluble resin makes the color material particles less likely to contact each other, and there are cases where dispersion stabilization occurs and the effect of the dispersant is reduced by this dispersion stabilization effect.

Examples of the other components include a surfactant for improving wettability, a silane coupling agent for improving adhesion, an antifoaming agent, a shrinkage inhibitor, an antioxidant, an anti-aggregating agent, and an ultraviolet absorber.

The color material dispersion liquid of the present invention is used as a pre-prepared product for preparing a photosensitive colored resin composition for a color filter, which will be described later. That is, the color material dispersion is a color material dispersion prepared in advance in the preparation of the photosensitive colored resin composition for a color filter, which will be described later, and having a high ratio of (mass of color material component in the composition)/(mass of solid component other than color material component in the composition). Specifically, the ratio of (mass of color material component in the composition)/(mass of solid component other than color material component in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid with the components described below, a photosensitive colored resin composition for a color filter having excellent dispersibility can be prepared.

< method for producing color Material Dispersion >

In the present invention, the method for producing the color material dispersion liquid is not particularly limited as long as the color material is dispersed in the solvent by the dispersant of the block copolymer or the salt-type block copolymer. Among them, from the viewpoint of excellent dispersibility and dispersion stability of the color material, any of the following 2 production methods is preferable.

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

In addition, the second method for producing a color material dispersion liquid of the present invention using a dispersant which is a salt-type block copolymer includes: and a step of mixing a solvent, the block copolymer, 1 or more compounds selected from the group consisting of the above general formulae (1) to (3), and a coloring material, and dispersing the coloring material while at least a part of the nitrogen site at the end of the constituent unit represented by the above general formula (I) forms a salt with the above compounds.

In the case of using a salt-type block copolymer, it is preferable from the viewpoint that the reaction end point and the reaction rate of the block copolymer before salt formation and 1 or more compounds in the group consisting of the general formulae (1) to (3) can be accurately confirmed, because the color material is dispersed by using the salt-type block copolymer as a dispersant after preparing the salt-type block copolymer according to the first production method.

Further, according to the second production method, since the dispersant of the salt block copolymer is prepared and the color material is dispersed, the salt block copolymer does not undergo self-aggregation, and the color material dispersion can be prepared efficiently and the dispersibility can be improved.

In the first and second manufacturing methods, the color material may be dispersed using an existing disperser.

Specific examples of the dispersing machine include roll mills such as a twin-roll mill and a three-roll mill, ball mills such as a ball mill and a vibration ball mill, and bead mills such as a paint conditioner, a continuous disc bead mill and a continuous ring bead mill. The preferred dispersing condition of the bead mill is that the diameter of the beads used is preferably 0.03 to 3.0mm, more preferably 0.05 to 2.0 mm.

Specifically, for example, pre-dispersion is performed using zirconia beads having a diameter of 2.0mm with a large bead diameter, and then main dispersion is performed using zirconia beads having a diameter of 0.1mm with a small bead diameter. After dispersion, filtration is preferably performed by a 0.5 to 2 μm filter.

I-2. the photosensitive colored resin composition for a color filter of the first aspect of the invention

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

The photosensitive colored resin composition for a color filter according to the first aspect of the present invention can form a colored layer having excellent color material dispersion stability, suppressed development residue, excellent development adhesion, excellent solvent resolubility, and excellent contrast by using the color material dispersion liquid according to the first aspect of the present invention.

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, and may further contain other components within a range not impairing the effects of the present invention. The components contained in the photosensitive colored resin composition for a color filter of the present invention will be described below, but the dispersant, the color material, and the solvent are the same as those described in the color material dispersion liquid of the present invention, and therefore, the description thereof will be omitted.

< alkali-soluble resin >

The alkali-soluble resin of the present invention has an acidic group, functions as a binder resin, and can be suitably selected from alkali-soluble resins that are soluble in a developer used for pattern formation, particularly preferably an alkaline developer.

The alkali-soluble resin preferred in the present invention is a resin having a carboxyl group as an acidic group, and specifically, there may be mentioned: acrylic copolymers having a carboxyl group, styrene-acrylic copolymers having a carboxyl group, epoxy (meth) acrylate resins having a carboxyl group, and the like. Among these, particularly preferred is an alkali-soluble resin having a carboxyl group in a side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain. The reason for this is that the film strength of the formed cured film can be improved by containing a photopolymerizable functional group. These acrylic copolymer, styrene-acrylic copolymer and epoxy acrylate resin may be used in combination of 2 or more.

The acrylic copolymer having a carboxyl group and the styrene-acrylic copolymer having a carboxyl group can be obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with an ethylenically unsaturated monomer other than the above.

Specific examples of the acrylic copolymer having a carboxyl group include those described in, for example, Japanese patent laid-open publication No. 2013-029832, and specific examples thereof include: copolymers of 1 or more selected from (meth) acrylic acid and anhydrides thereof and monomers having no carboxyl group such as methyl (meth) acrylate and ethyl (meth) acrylate. Examples of the polymer include, but are not limited to, polymers obtained by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above-mentioned copolymer to introduce an ethylenically unsaturated bond.

Among these, addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is particularly preferable from the viewpoint of more stable sensitivity and film strength of the colored layer.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, if the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film in an alkaline developer is lowered, and pattern formation becomes difficult. When the copolymerization ratio exceeds 50% by mass, pattern deletion or film roughness on the pattern surface tends to occur easily when developed with an alkali developing solution.

The preferable weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When the weight average molecular weight is less than 1,000, the binder function after curing is remarkably reduced, and when the weight average molecular weight exceeds 50,000, pattern formation may be difficult when development is performed with an alkaline developer.

The weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by Shodex GPC System-21H (Shodex GPC System-21H) using polystyrene as a standard substance and THF as an eluent.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, but an epoxy (meth) acrylate compound obtained by reacting a reactant of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride is suitable.

The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known compounds and used.

Among epoxy (meth) acrylate resins having a carboxyl group, an epoxy (meth) acrylate resin having a carboxyl group, which contains a structure (Cardo structure) in which two benzene rings are bonded to a fluorene skeleton represented by the following chemical formula (a) in the molecule, is preferable from the viewpoint of improving the effect of suppressing defects, improving the curability of the colored layer, and increasing the residual film ratio of the colored layer.

[ chemical formula 5]

The exact mechanism of the epoxy (meth) acrylate resin having a carboxyl group containing the Cardo structure (hereinafter referred to as Cardo resin) is not yet elucidated, but it is considered that since the fluorene skeleton contains pi-conjugated system, it has high sensitivity to radicals, and by combining the oxime ester photoinitiator described later with the Cardo resin, it is possible to improve required performances such as sensitivity, developability, and development adhesion. Further, the Cardo resin is preferable from the viewpoint that a colored resin composition free from aggregates can be designed even at a high color density because of its high solvent re-solubility.

Examples of the Cardo resin include polymerizable compounds represented by the following general formula (B) described in japanese patent laid-open publication No. 2007-119720, and reaction products (condensates) of epoxy group (meth) acrylate resins having a fluorene skeleton and polybasic acids described in japanese patent laid-open publication No. 2006-308698.

[ chemical formula 6]

(in the general formula (B), X represents a group represented by the following general formula (D), Y represents a polycarboxylic acid or an acid anhydride thereof, and R representsⁱRepresents a group represented by the following general formula (C), j is an integer of 0 to 4, k is an integer of 0 to 3, and n is an integer of 1 or more. )

[ chemical formula 7]

(in the above general formula (C), RⁱⁱRepresents a hydrogen atom or a methyl group, RⁱⁱⁱEach independently represents a hydrogen atom or a methyl group. )

[ chemical formula 8]

(in the above general formula (D), R^ivEach independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, R^vrepresents-O-or-OCH₂CH₂O-。)

The Cardo resin used in the present invention can be obtained by, for example, epoxidizing a fluorene bisphenol compound to obtain an epoxy compound of the fluorene bisphenol compound, reacting the epoxy compound with (meth) acrylic acid to obtain an epoxy group (meth) acrylate resin, and reacting the epoxy group (meth) acrylate resin with a polybasic acid or an acid anhydride thereof.

As the fluorene bisphenol compound, there may be exemplified the compound represented by the general formula (D) wherein R is^vis-O-, preferably the fluorene bisphenol compound in which the-O-is-OH.

Examples of the fluorene bisphenol compound include 9, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene, bisphenol compounds such as 9, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, and mixtures thereof.

Examples of the polybasic acid and the acid anhydride thereof used for the reaction of the epoxy (meth) acrylate resin having a fluorene skeleton include dicarboxylic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, chlorendic acid, methyltetrahydrophthalic acid, and glutaric acid, and acid anhydrides thereof; tetracarboxylic acids such as biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylether tetracarboxylic acid, biphenylsulfone tetracarboxylic acid, 4- (1, 2-dicarboxyethyl) -1, 2, 3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, and acid dianhydrides thereof; tricarboxylic acids such as trimellitic acid and anhydrides thereof, and anhydrides thereof. These can be used alone, also can be used in combination of 2 or more.

The Cardo resin used in the present invention preferably includes, for example, an epoxy (meth) acrylate acid adduct having a fluorene skeleton, which is an addition product of a fluorene epoxy (meth) acrylic acid derivative and a dicarboxylic anhydride and/or a tetracarboxylic dianhydride.

A trade name of a commercially available Cardo resin usable in the present invention includes INR-16M (manufactured by Nagase ChemteX).

The epoxy (meth) acrylate resin having a carboxyl group may be used alone in 1 kind or in combination of 2 or more kinds.

The alkali-soluble resin used in the photosensitive colored resin composition for a color filter may be used alone in 1 kind, or may be used in combination with 2 or more kinds, and the content thereof is not particularly limited, and the alkali-soluble resin is preferably in the range of 5 to 60 mass%, more preferably 10 to 40 mass%, relative to the total solid content of the photosensitive colored resin composition for a color filter. If the content of the alkali-soluble resin is less than the lower limit, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is more than the upper limit, film roughening or pattern deletion may occur during development. In the present invention, the solid component is not limited to the above-mentioned solvent, and includes liquid polyfunctional monomers 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 is a polyfunctional monomer polymerizable by a photoinitiator described later, and a compound having 2 or more ethylenically unsaturated double bonds is usually used, and a polyfunctional (meth) acrylate having 2 or more acryloyl groups or methacryloyl groups is particularly preferable.

Such a polyfunctional (meth) acrylate can be appropriately selected from conventionally known ones and used. Specific examples thereof include polyfunctional (meth) acrylates described in Japanese patent application laid-open No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition for a color filter of the present invention, the polyfunctional monomer is preferably a poly (meth) acrylate of a polyol having 3 (trifunctional) or more polymerizable double bonds, more preferably 3 or more atoms, or a dicarboxylic acid modification thereof, and specifically preferably: trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, succinic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The content of the above-mentioned polyfunctional monomer used in the photosensitive colored resin composition for a color filter is not particularly limited, but the polyfunctional monomer is preferably in the range of 5 to 60 mass%, more preferably 10 to 40 mass%, relative to the total solid content of the photosensitive colored resin composition for a color filter. If the content of the polyfunctional monomer is less than the lower limit, the photocuring may not be sufficiently performed, and the exposed portion may be eluted during development, and if the content of the polyfunctional monomer is more than the upper limit, the alkali developability may be reduced.

< photoinitiator >

The photoinitiator used in the photosensitive colored resin composition for a color filter is not particularly limited, and 1 kind of photoinitiator or a combination of 2 or more kinds of photoinitiators can be used from among conventional ones. Specific examples thereof include photoinitiators described in Japanese patent laid-open publication No. 2013-029832.

The photoinitiator may be used alone in 1 kind or in combination of two or more kinds. Among them, the oxime ester photoinitiator is preferably contained from the viewpoint of having a high effect of suppressing the occurrence of pattern deletion and a high effect of suppressing the occurrence of water bleeding. When a dispersant having an acid value is used, water bleeding tends to occur particularly easily, but the use of an oxime ester photoinitiator in combination is preferable from the viewpoint that the occurrence of water bleeding can be suppressed. The term "water bleeding" refers to a phenomenon in which a trace such as water bleeding occurs after alkali development and rinsing with pure water. This water bleeding disappears after the post-baking, and therefore, the water bleeding does not cause any problem as a product, but the water bleeding is detected as a non-uniform abnormality in the appearance inspection of the pattern surface after the development, and a problem arises that a normal product and an abnormal product cannot be distinguished from each other. Therefore, if the inspection sensitivity of the inspection apparatus is lowered during the appearance inspection, the yield of the final color filter product is lowered as a result, which is problematic.

Among these, an oxime ester photoinitiator having an aromatic ring is preferable, an oxime ester photoinitiator having a condensed ring containing an aromatic ring is more preferable, and an oxime ester photoinitiator having a condensed ring containing a benzene ring and a heterocycle is even more preferable, from the viewpoint of reducing contamination of the photosensitive colored resin composition for a color filter or device contamination due to decomposition products.

The oxime ester photoinitiator may be suitably selected from 1, 2-octanedione-1- [4- (phenylthio) -, 2- (o-benzoyl) ], ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime), oxime ester photoinitiators described in Japanese patent laid-open Nos. 2000-80068, 2001-233842, 2010-527339, 2010-527338, 2013-041153, and the like. As commercially available products, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (manufactured by BASF Co., Ltd.), ADEKA OPT-N-1919, ADEKAARKLS NCI-930, ADEKA ARKLS NCI-831 (manufactured by ADEKA Co., Ltd.), TR-PBG-304, TR-PBG-326, and TR-PBG-3057 (manufactured by Changzhou super New electronic Material Co., Ltd.) can be used.

The oxime ester photoinitiator used in the present invention is preferably an oxime ester photoinitiator that generates an alkyl radical, more preferably a methyl radical, from the viewpoint that the photoinitiator is excellent in curability even for a photosensitive colored resin composition in which the color material concentration is increased in order to realize a wide color gamut by using PG59 and is excellent in development resistance, an effect of suppressing the occurrence of pattern deletion, and an effect of suppressing the occurrence of water bleeding. It is presumed that the alkyl radical is more likely to activate radical rotation than the aryl radical. Examples of the oxime ester photoinitiator that generates an alkyl radical include ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, [8- [ [ (acetoxy) imino ] [2- (2, 2, 3, 3-tetrafluoropropoxy) phenyl ] methyl ] -11- (2-ethylhexyl) -11H-benzo [ a ] carbazol-5-yl ] -, (2, 4, 6-trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), ethanone, 1- [ 9-ethyl-6- (1, 3-dioxolane, 4- (2-methoxyphenoxy) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) (trade name ADEKA OPT-N-1919, manufactured by ADEKA Co., Ltd.), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy-2-methylphenyl ] -, o-acetyloxime) (trade name ADEKAAKLS NCI-831, manufactured by ADEKA Co., Ltd.), 1-propanone, 3-cyclopentyl-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) (trade name TR-PBG-304, changzhou powerful new electronic material Co., Ltd.), 1-acetone, 3-cyclopentyl-1- [2- (2-pyrimidylthio) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) (trade name TR-PBG-314, manufactured by Changzhou powerful new electronic material Co., Ltd.), ethanone, 2-cyclohexyl-1- [2- (2-pyrimidinyloxy) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) (trade name TR-PBG-326, manufactured by Changzhou powerful new electronic material Co., Ltd.), ethanone, 2-cyclohexyl-1- [2- (2-pyrimidinylthio) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) (trade name TR-PBG-331, manufactured by Changzhou powerful new electronic materials Co., Ltd.), 1-octanone, 1- [4- [3- [1- [ (acetoxy) imino ] ethyl ] -6- [4- [ (4, 6-dimethyl-2-pyrimidinyl) thio ] -2-methylbenzoyl ] -9H-carbazol-9-yl ] phenyl ] -, 1- (o-acetyloxime) (trade name EXTA-9, manufactured by UNIONCHEMICAL Co., Ltd.), and the like.

In addition, in the oxime ester photoinitiator, a photoinitiator having a 3-stage amine structure is preferably used in combination from the viewpoint of improving sensitivity. This is because the photoinitiator having a 3-stage amine structure has a 3-stage amine structure as an oxygen quencher in the molecule, and therefore, radicals generated from the initiator are less likely to be deactivated by oxygen, and the sensitivity can be improved. Examples of commercially available products of the photoinitiator having a 3-stage amine structure include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (e.g., Irgacure907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (e.g., Irgacure369, manufactured by BASF), and 4, 4' -bis (diethylamino) diphenylketone (e.g., Hicure ABP, manufactured by chuanxiong).

The content of the photoinitiator used in the photosensitive colored resin composition for a color filter is not particularly limited, and the photoinitiator is preferably within a range of 3 to 40% by mass, more preferably 10 to 30% by mass, based on the total solid content of the photosensitive colored resin composition for a color filter. If the content is less than the lower limit, the photocuring may not be sufficiently performed, and the exposed portion may be eluted during the development; on the other hand, if the amount is more than the above upper limit, yellowing of the obtained colored layer may be increased, and luminance may be lowered.

< optional additional Components >

The photosensitive colored resin composition for a color filter may contain various additives as required.

Examples of the additive include, in addition to an antioxidant, a polymerization stopper, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.

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 conventional ones. Specific examples of the antioxidant include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like, and hindered phenol antioxidants are preferably used from the viewpoint of heat resistance.

When an antioxidant is used, the amount of the antioxidant to be blended is not particularly limited as long as the effect of the present invention is not impaired, and the amount of the antioxidant to be blended is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 4.0% by mass, based on the total amount of solid components in the photosensitive colored resin composition for a color filter. When the content is not less than the lower limit, the heat resistance is excellent. On the other hand, if the value is less than the upper limit, the photosensitive colored resin composition for a color filter of the present invention can be a photosensitive colored resin composition for a color filter with high sensitivity.

Specific examples of the surfactant and the plasticizer include those described in Japanese patent laid-open publication No. 2013-029832.

< blending ratio of respective components in photosensitive colored resin composition for color Filter >

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 a color filter. When the lower limit is not less than the above lower limit, the color 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). When the content is less than the above upper limit, a colored layer having sufficient hardness and adhesion to a substrate can be obtained while having excellent storage stability. In particular, when forming a colored layer having a high color material concentration, the content of the color material is preferably 15 to 65% by mass, more preferably 25 to 60% by mass, based on the photosensitive colored resin composition for a color filter.

The content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed, and for example, 1 to 40% by mass can be used based on the total solid content of the photosensitive colored resin composition for a color filter. The amount of the solid content of the photosensitive colored resin composition for a color filter is preferably 2 to 30% by mass, and particularly preferably 3 to 25% by mass. When the lower limit value is not less than the above lower limit value, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive colored resin composition for a color filter is further excellent. When the content is not more than the above upper limit, the developability is good. Particularly, when forming a colored layer having a high color material concentration, the content of the dispersant is preferably 2 to 25% by mass, more preferably 3 to 20% by mass, based on the photosensitive colored resin composition for a color filter. In the case of a salt-type block copolymer, the mass of the dispersant is the total mass of the block copolymer before salt formation and 1 or more compounds of the group consisting of the general formulae (1) to (3).

The content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. The amount of the solvent is preferably 55 to 95% by mass, more preferably 65 to 88% by mass, based on the total amount of the photosensitive colored resin composition for a color filter. When the content of the solvent is within the above range, a product having excellent coatability can be obtained.

< 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 photosensitive colored resin composition can be obtained by adding an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and other components as needed to the color material dispersion of the present invention, and mixing them by using a known mixing means.

I-3. color Filter of first aspect of the invention

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

The color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. Referring to fig. 1, a color filter 10 of the present invention includes a transparent substrate 1, a light-shielding portion 2, and a colored layer 3.

< colored layer >

The colored layer used in the color filter of the present invention is formed by curing the photosensitive colored resin composition for a color filter of the present invention.

The colored layer is usually formed in an opening of a light shielding portion on a transparent substrate described later, and is usually formed of a colored pattern of 3 colors or more.

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 delta type, or a 4-pixel arrangement type. The width, area, and the like of the colored layer can be set arbitrarily.

The thickness of the colored layer is suitably controlled by adjusting the coating method, the solid content concentration or viscosity of the photosensitive colored resin composition for a color filter, and the like, and is preferably in the range of 1 to 5 μm in general.

The colored layer can be formed by the following method, for example.

First, the photosensitive colored resin composition for a color filter of the present invention is applied to a transparent substrate to be described later by a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method, to form a wet coating film. Among them, spin coating and die coating can be preferably used.

Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, and a cured coating film is formed by photopolymerization of an alkali-soluble resin and a polyfunctional monomer or the like. Examples of the light source used for the exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and electron beams. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.

In addition, after exposure, a heat treatment may be performed to promote 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 to be used, the thickness of a coating film, and the like.

Then, a developing treatment is performed using a developing solution to dissolve and remove the unexposed portion, thereby forming a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. To this alkali solution, a proper amount of a surfactant or the like may be added. In addition, a general method can be used for the development method.

After the development treatment, the cured coating film of the photosensitive colored resin composition for a color filter is usually dried by washing with a developer to form a colored layer. After the development treatment, a heating treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and may be appropriately selected according to the application of the coating film.

< light-shielding part >

The light-shielding portion in the color filter of the present invention is a light-shielding portion formed in a pattern on a transparent substrate described later, and may be the same as the light-shielding portion used as the 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, a matrix shape, and the like. The light shielding portion may be a thin metal film of chromium or the like formed by sputtering, vacuum deposition, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of the 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, and the like.

The thickness of the light-shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and is set to about 0.5 to 2 μm in the case of dispersing or dissolving a black pigment in a binder resin.

< transparent substrate >

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples thereof include transparent rigid materials having no flexibility, such as quartz glass, alkali-free glass, and synthetic quartz plate; or a transparent flexible material having flexibility such as a transparent resin film, an optical resin plate, and flexible glass.

The thickness of the transparent substrate is not particularly limited, and, for example, a transparent substrate of about 100 μm to 1mm can be used according to the application of the color filter of the present invention.

In addition to the transparent substrate, the light-shielding portion, and the colored layer, the color filter of the present invention may have a protective layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, and the like.

I-4. liquid crystal display device of first aspect of the present invention

A liquid crystal display device according to a first aspect of the present invention is characterized by having the color filter according to the first aspect of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

With respect to such a liquid crystal display device of the present invention, description is made with reference to the drawings. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in fig. 2, a liquid crystal display device 40 of the present invention has: a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

The liquid crystal display device of the present invention is not limited to the structure shown in fig. 2, and may be a structure known for liquid crystal display devices used as general color filters.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used for a general liquid crystal display device 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 suitably used.

In addition, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

As the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention and the like.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include: vacuum injection, liquid crystal dropping, and the like.

In the vacuum injection method, for example, a liquid crystal cell is prepared using a color filter and a counter substrate in advance, an isotropic liquid is prepared by heating the liquid crystal, the liquid crystal is injected into the liquid crystal cell in the state of the isotropic liquid by a capillary effect, and the liquid crystal layer is sealed with an adhesive. Thereafter, the liquid crystal cell is slowly cooled to room temperature, whereby the enclosed liquid crystal can be aligned.

In the liquid crystal dropping method, for example, a sealant is applied to the edge of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes an isotropic phase, the liquid crystal is dropped in the state of an isotropic liquid using a dispenser or the like, the color filter and the counter substrate are stacked under reduced pressure, and the liquid crystal layer is bonded via the sealant. Thereafter, the liquid crystal cell is slowly cooled to room temperature, and the enclosed liquid crystal can be aligned.

I-5. organic light emitting display device of first aspect of the present invention

An organic light emitting display device of a first aspect of the present invention is characterized by having: the color filter and the organic light-emitting body of the present invention are described above.

With respect to such an organic light emitting display device of the present invention, description is made with reference to the accompanying 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 has a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

Examples of the method for stacking the organic light-emitting bodies 80 include: a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter; a method of bonding the organic light-emitting body 80 formed on the other substrate to the inorganic oxide film 60. In the organic light-emitting body 80, any of 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, and other structures can be used as appropriate. The organic light-emitting display device 100 thus manufactured can be applied to, for example, a passive drive type organic EL display or 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 known structure of an organic light emitting display device used as a general color filter.

Second aspect of the invention

The color material dispersion for a color filter, the photosensitive colored resin composition for a color filter, the liquid crystal display device, and the organic light emitting display device according to the second aspect of the present invention will be described in order below.

II-1. color material dispersion liquid according to the second aspect of the present invention

(i) First embodiment of the second aspect of the present invention

A color material dispersion liquid for a color filter according to a first aspect of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent,

the color material contains c.i. pigment green 59;

the dispersant is a polymer having a constituent unit represented by the following general formula (I).

[ chemical formula 9]

In the color material dispersion liquid according to the first embodiment of the second aspect of the present invention, since the color material contains c.i. pigment green 59 (hereinafter, may be abbreviated as PG59) and a polymer having a constituent unit represented by general formula (I) is used in combination as a dispersant, a green color material dispersion liquid exhibiting bluish green color, excellent color material dispersion stability, and high luminance can be obtained.

In the second aspect of the present invention, PG59 is used as a coloring material, so that a chromaticity region that cannot be realized by PG58 can be realized, and further, a polymer having a constituent unit represented by general formula (I) is used in combination, so that a color filter having a large triangle formed by connecting 3 points of red, green, and blue pixels and excellent color reproducibility can be obtained while achieving high luminance and high contrast.

In addition, in the color material dispersion liquid according to the first embodiment of the second aspect of the present invention, since PG59 is combined with a polymer having a constitutional unit represented by general formula (I) as a dispersant, a photosensitive colored resin composition having excellent color material dispersion stability and excellent solvent re-solubility can be produced. Since the polymer having the constitutional unit represented by the general formula (I) is combined with the PG 59-containing color material as the dispersant, it is estimated that the PG 59-containing color material strongly adsorbed to the nitrogen site contained in the constitutional unit represented by the general formula (I) is easily washed away by the redissolved solvent in a state adsorbed to the dispersant while the color material containing PG59 is strongly adsorbed to the nitrogen site to thereby improve the dispersibility of the color material. In addition, when a polymer having a constituent unit represented by general formula (I) is combined as a dispersant in a color material containing PG59, the generation of development residue tends to be easily suppressed. The reason for this is presumed that the color material containing PG59 which is strongly adsorbed to the nitrogen site and surrounded by the dispersant is easily washed off in a state adsorbed to the dispersant during development, and the generation of development residue is easily suppressed without leaving the color material on the base material.

(ii) Second aspect of the present invention

A color material dispersion liquid for a color filter according to a second aspect of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent,

the color material contains C.I. pigment green 59 and yellow color material;

the dispersant may be a polymer having a constituent unit represented by the general formula (I).

In the color material dispersion liquid according to the second embodiment of the second aspect of the present invention, since the color material contains PG59 and a yellow color material and a polymer having a constituent unit represented by general formula (I) is used in combination as a dispersant, a colored layer having excellent color material dispersion stability, high luminance and excellent color reproducibility can be formed while suppressing occurrence of display failure.

In the second aspect of the present invention, PG59 used as a coloring material is a single color, exhibits bluish green, has strong coloring power, and has high luminance, and therefore, by combining with a yellow coloring material, it is possible to produce a green pixel contained in the green region having a high color density even if the content of PG59 in the coloring material is suppressed, or the ratio of the P/V ratio ((the mass of the coloring material component in the composition)/(the mass of the solid component other than the coloring material component in the composition)) is suppressed. However, when the color material dispersion liquid of the present invention is used, the content of the green color material having a phthalocyanine skeleton in the pixel can be reduced, and the above-mentioned P/V ratio can be reduced, so that it is estimated that a green pixel in which the occurrence of a display failure is suppressed can be realized.

In addition, PG59 used as a color material in the second aspect of the present invention can realize a chromaticity region that PG58 cannot realize in the green chromaticity region of the high color density. In the second embodiment of the second aspect of the present invention, PG59 and a yellow color material are used in combination with a polymer having a constituent unit represented by general formula (I), so that the color material dispersibility and the color material dispersion stability are excellent, and thus a color filter having a large triangle formed by connecting 3 points of red, green, and blue pixels and excellent color reproducibility can be obtained while achieving high luminance and high contrast.

In addition, in the color material dispersion liquid according to the second embodiment of the second aspect of the present invention, since the polymer having the structural unit represented by the general formula (I) is combined as the dispersant in the PG59 and the yellow color material, the photosensitive colored resin composition having excellent solvent re-solubility can be produced. It is presumed that since PG59 and the yellow color material are combined with a polymer having a structural unit represented by general formula (I) as a dispersant, PG59 and the yellow color material, which are strongly adsorbed to a nitrogen site and surrounded by the dispersant, are easily washed away by a re-soluble solvent in a state of being adsorbed to the dispersant.

In the color material dispersion liquid for a color filter according to the second embodiment of the second aspect of the present invention, it is preferable that PG59 is contained in an amount of 5 to 95 mass% in the color material from the viewpoint of suppressing the occurrence of display defects and increasing color reproducibility and luminance.

In the color material dispersion liquid for a color filter according to the second embodiment of the present invention, in order to easily form a colored layer having high luminance and high contrast and excellent color reproducibility while suppressing the occurrence of display defects, the yellow color material is preferably at least 1 selected from the group consisting of c.i. pigment yellow 138 (hereinafter, may be abbreviated as PY138), c.i. pigment yellow 139 (hereinafter, may be abbreviated as PY139), c.i. pigment yellow 185 (hereinafter, may be abbreviated as PY185), c.i. pigment yellow 150 (hereinafter, may be abbreviated as PY150), and a pigment derivative thereof.

In the color material dispersion liquid for a color filter according to the second embodiment of the second aspect of the present invention, the color material preferably contains at least 1 of c.i. pigment green 58 and c.i. pigment green 7 in addition to PG 59. Among them, PG58 is preferably contained in addition to PG59 in order to achieve a target chromaticity, suppress display defects, and form a green pixel with high luminance. On the other hand, from the viewpoint of achieving a target chromaticity, suppressing display defects, further reducing the P/V ratio, improving platemaking properties such as development resistance, and the like, it is preferable to contain PG7 in addition to PG 59. In addition, from the viewpoint of achieving a target chromaticity, suppressing a display failure, and improving the balance between luminance and improving platemaking property due to the reduction in the P/V ratio, it is preferable to include PG58 and PG7 in addition to PG 59.

(iii) Third aspect of the second aspect of the present invention

A color material dispersion liquid for a color filter of a third embodiment of the present invention is a color material dispersion liquid for a color filter containing a color material, a dispersant, and a solvent,

the color material contains C.I. pigment green 59, blue color material and yellow color material; the yellow color material is (Y1) containing at least 1 yellow color material of c.i. pigment yellow 185, or (Y2) containing c.i. pigment yellow 139 as an essential component, and further containing at least 1 or more yellow color materials of at least 2 selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150 and derivatives thereof;

In the color material dispersion liquid according to the third embodiment of the second aspect of the present invention, since the specific color material is contained and the polymer having the structural unit represented by the general formula (I) is used in combination as the dispersant, a colored layer having excellent color material dispersion stability, high luminance and excellent color reproducibility can be formed while suppressing the occurrence of display defects.

According to the color material dispersion liquid of the third embodiment of the second aspect of the present invention, it is estimated that by combining any one of the above (Y1) or (Y2) as a yellow color material with PG59 and a blue color material, a wavelength portion which is not sufficiently absorbed by PG59 and the blue color material can be efficiently absorbed, the total amount of the color materials can be reduced, and the above P/V ratio can be reduced to reproduce a color. Therefore, in the green color of the high color density, a region (x is 0.14 to 0.30, and y is 0.61 to 0.75) which is green of the high color density, and further (x is 0.14 to 0.30, and y is 0.66 to 0.75) can be realized, and a colored layer with high luminance in which display failure is suppressed can be formed.

In addition, since the specific yellow color material has excellent dispersibility when combined with a specific dispersant described later, it is possible to easily improve the contrast and to produce a photosensitive colored resin composition having excellent solvent re-solubility.

In the color material dispersion liquid according to the third embodiment of the second aspect of the present invention, the blue color material preferably contains at least 1 of c.i. pigment blue 15:3 and c.i. pigment blue 15:4 from the viewpoint of brightness.

The color material dispersion liquid according to the second aspect of the present invention is a color material dispersion liquid containing at least a color material, a dispersant and a solvent, and may further contain other components within a range not impairing the effects of the present invention.

The respective components of the color material dispersion liquid according to the second aspect of the present invention will be described in detail in the following order.

< color Material >

In the second aspect of the present invention, the coloring material contains c.i. pigment green 59 as a zinc phthalocyanine pigment.

PG59 is a color material that can represent x 0.10 to 0.30 and y 0.30 to 0.64, and is particularly a color material characterized by x 0.13 to 0.20 and y 0.32 to 0.60, as chromaticity coordinates in the XYZ colorimetric system of JIS Z8701 in which color measurement is performed using a C light source alone.

PG59 is characterized by being able to represent an xy chromaticity coordinate region surrounded by the following

equations

1, 2, and 3 in the XYZ color system of JIS Z8701 in which the color measured by the C light source is used alone.

(equation 1)

y＝6.715×x-0.286

Wherein, in equation 1, x is more than 0.121 and less than 0.133

(equation 2)

y＝7147.200×x⁵-8466.000×x⁴+3891.400×x³-854.200×x²+86.380×x-2.579

Wherein, in equation 2, 0.133 < x < 0.310

(equation 3)

y＝1189.500×x⁶+1817.000×x⁵-3011.300×x⁴+1447.800×x³-307.420×x²+27.628×x-0.285

Wherein, in equation 3, 0.121 < x < 0.310

Among the xy chromaticity coordinate regions enclosed by the

above equations

1, 2 and 3, the region where x is 0.13 to 0.20 and y is 0.32 to 0.60 is most characteristic and effective.

PG59 used in the present invention has a wavelength (Tmax) of 505 to 535nm at which the transmittance of the spectral transmittance spectrum at 400 to 700nm becomes maximum, when the transmittance at 450nm is 5%. Further, the transmittance at the wavelength (Tmax) is 70% or more. PG59 used in the present invention has a transmittance of 15% or less in the spectral transmittance spectrum at 435nm and a transmittance of 5% or less in the spectral transmittance spectrum at 575 nm.

In order to coat PG59 alone and measure color, a coating solution is prepared by blending a suitable dispersant, binder component and solvent in PG59, and the coating solution is applied to a transparent substrate, dried and cured as necessary. As the binder component, a non-curable thermoplastic resin composition may be used, or a photocurable (photosensitive) or thermosetting resin composition may be used, provided that a transparent coating capable of color measurement can be formed. In the photosensitive colored resin composition of the present invention described later, a coating film containing only PG59 as a coloring material can be formed and measured by using a composition containing only PG59 as a coloring material.

The transparent coating film containing a dispersant and a binder component and capable of color measurement can be characterized by having a spectral transmittance at a film thickness of 2.0 μm and a spectral transmittance at 380 to 780nm of 95% or more, for example.

The spectral transmittance spectrum can be measured using a spectroscopic measurement apparatus (for example, Olympus microscopy apparatus OSP-SP 200). The measurement conditions were C illuminant.

In the color material dispersion liquid of the present invention, PG59 alone may be used as the color material. On the other hand, a color material different from PG59 as exemplified in the color material items of the color material dispersion liquid according to the first aspect of the present invention may be combined as another color material in PG59 without impairing the effects of the present invention. As the other color material, for example, other green color material, yellow color material, and blue color material can be suitably used.

In the case where a different color material other than PG59 is used in the color material dispersion liquid according to the second aspect of the present invention, the content of PG59 may be appropriately adjusted depending on the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of increasing color reproducibility and luminance, PG59 is preferably contained in an amount of 5 mass% or more, more preferably 10 mass% or more, based on the entire color material containing PG 59.

In the color material dispersion liquid according to the second aspect of the present invention, it is preferable to use a yellow color material in combination with PG59 as the color material, from the viewpoint of suppressing the occurrence of display failure in green pixels and forming a colored layer having high luminance and excellent color reproducibility (the second embodiment of the second aspect of the present invention).

Examples of the yellow color material include 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, 185, and c.i. pigment yellow 150.

Specific examples of the derivative pigment of c.i. pigment yellow 150 include metal complexes of mono-, di-, tri-and tetraanions of azo compounds represented by the following formula (i) or following one of their tautomeric structures, which act as the main component of at least 1 guest compound, and metals, for example, Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn, and La. Among the metals, Ni is preferable, and at least 1 of the derivative pigment of the c.i. pigment yellow 150 containing Ni and Zn and the derivative pigment of the c.i. pigment yellow 150 containing Ni and Cu is more preferable. Among them, at least 1 of the c.i. pigment yellow 150 derivative pigment containing Ni and Zn at a ratio (molar ratio) of 8:2 to 2: 8 is preferable, and the c.i. pigment yellow 150 derivative pigment containing Ni and Zn at a ratio (molar ratio) of 5: 5 to 9.8: 0.2 is preferable.

[ chemical formula 10]

Chemical formula (i)

(in the above chemical formula (i), R is OH or NH independently₂NH-CN, acylamino or arylamino, R' are each independently-OH or-NH₂。)

The C.I. pigment yellow 150 and its derivative pigment can be obtained by referring to Japanese patent laid-open Nos. 2001-354869, 2005-325350, 2007-25687, 2007-23287, 2007-23288 and 2008-24927.

Further, commercially available products can be suitably used as the yellow color material.

In the color material dispersion liquid according to the second aspect of the present invention, the yellow color material is appropriately selected, and 1 kind of the yellow color material may be used alone or 2 or more kinds of the yellow color material may be used in combination. The preferred yellow color material is preferably the same as that used for the photosensitive colored resin composition for a color filter described later, for the same reason.

In the dispersion liquid of the color material according to the second embodiment of the second aspect of the present invention, other color materials exemplified by the photosensitive colored resin composition described later may be used in combination with PG59 and the yellow color material, without impairing the effects of the present invention. As the other color material, for example, other green color material, blue color material, orange color material, or the like can be suitably used. Examples of the green coloring material different from PG59 include phthalocyanine green pigments such as PG58, PG7, and PG 36. The other preferable color material is preferably the same one for the same reason as described in the photosensitive colored resin composition for a color filter described later.

In the case where the color material dispersion liquid according to the second aspect of the present invention further contains another green color material, it is preferable to use PY138 in combination with at least 1 of the pigments of PY150 and its derivative in the yellow color material from the viewpoint of suppressing the occurrence of display defects and easily realizing a colored layer with high luminance.

In the color material dispersion liquid according to the second embodiment of the second aspect of the present invention, the content ratio of PG59 to the entire color material, the content ratio of the yellow color material to PG59, and the content ratio when PG59, the yellow color material, and other color materials are used are preferably the same as those of the photosensitive coloring resin composition described later. However, since the photosensitive colored resin composition can be produced by appropriately mixing 2 or more kinds of the color material dispersion liquid, the photosensitive colored resin composition can be appropriately used without setting the content ratio to be the same as that of the photosensitive colored resin composition described later.

In the color material dispersion liquid according to the second aspect of the present invention, a blue color material and a yellow color material are combined as a color material in PG59, and the yellow color material preferably contains (Y1) at least 1 yellow color material of PY 185; or (Y2) further contains 1 or more kinds of at least 2 kinds of yellow color materials selected from the group consisting of PY138, PY150, and a derivative pigment of PY150, with PY139 as an essential component (third embodiment of the second aspect of the present invention).

In the present invention, the blue color material is a color material having a peak top in a range of 435nm to 490nm when the spectral transmittance spectrum is measured in the same manner as described in the case of PG 59.

Examples of the blue coloring material include c.i. pigment blue 15, 15:3, 15:4, 15:6, and 60. Among the dispersible dyes described in the photosensitive colored resin composition described later, a color material falling within the range of the blue color material can be appropriately selected and used.

In the color material dispersion liquid according to the third embodiment of the second aspect of the present invention, the blue color material is appropriately selected, and 1 kind of the blue color material may be used alone or 2 or more kinds of the blue color material may be used in combination.

Among them, in the case where PG59 and the specific yellow color material are combined, the β type copper phthalocyanine pigment is preferable, in which at least 1 of c.i. pigment blue 15:3 and c.i. pigment blue 15:4 is preferably contained, and the β type copper phthalocyanine pigment is preferably contained in an amount of 60 to 100 mass% in the total amount of the blue color material, from the viewpoint of suppressing a decrease in luminance or from the viewpoint of excellent dispersibility when the specific dispersant is combined, as the blue color material used in the third embodiment of the second aspect of the present invention.

Among them, from the viewpoint of brightness, the blue color material is preferably at least 1 of c.i. pigment blue 15:3 and c.i. pigment blue 15: 4.

In the third embodiment of the second aspect of the present invention, (Y1) contains at least 1 yellow color material of PY185, and may further contain another yellow color material in addition to PY185, and examples of the yellow color material include derivative pigments of PY1, 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, and PY 150.

In the third embodiment of the second aspect of the present invention, as the yellow color material to be combined with PY185, 1 or more selected from the group consisting of PY139, PY150, and a pigment derivative thereof is preferable from the viewpoint of excellent color material dispersion stability, suppression of occurrence of display failure, and easy realization of a colored layer having high luminance and excellent color reproducibility.

In the third embodiment of the second aspect of the present invention, (Y2) contains PY139 as an essential component, and further contains 1 or more kinds of at least 2 kinds of yellow color materials selected from the group consisting of PY138, PY150 and a pigment derivative thereof, and may further contain other yellow color materials in addition to the above-mentioned at least 2 kinds of yellow color materials, and examples of the yellow color materials include PY1, 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, 151, 152, 153, 154, 155, 156, 166, 168, 175 and the like.

In the third embodiment of the second aspect of the present invention, it is preferable to use (Y1) as the yellow color material because higher luminance can be easily achieved. On the other hand, when the yellow color material is used as the above (Y2), high contrast can be easily achieved, which is preferable.

In the third embodiment of the second aspect of the present invention, the (Y2) contains PY139 as an essential component, and further contains 1 or more kinds of at least 2 kinds of yellow color materials selected from the group consisting of PY138, PY150, and a pigment derivative thereof, and among them, it is preferable to contain PY139 as an essential component, and further contain 1 or more kinds of at least 2 kinds of yellow color materials selected from the group consisting of PY150 and a pigment derivative thereof, from the viewpoint of suppressing the occurrence of display defects and easily realizing a colored layer having high luminance and high contrast.

In the dispersion liquid of the color material according to the third embodiment of the second aspect of the present invention, other color materials exemplified by the photosensitive colored resin composition described later may be used in combination with the PG59, the blue color material, and the specific yellow color material, without impairing the effects of the present invention. As the other color material, for example, other green color material, orange color material, or the like can be suitably used. As the appropriate other color material, the same other color material is preferably used for the same reason as described in the photosensitive colored resin composition for a color filter described later. In the present invention, the green color material refers to a green color material having a peak top in a range of more than 490nm and 580nm or less as a standard when the spectral transmittance spectrum is measured as described above.

In the dispersion liquid of a color material according to the third embodiment of the second aspect of the present invention, the content ratios of each of PG59, the blue color material, and the yellow color material, and the content ratio when another color material is used, are preferably the same as those of the photosensitive coloring resin composition described later. Among these, since the photosensitive colored resin composition can be produced by appropriately mixing and using 2 or more kinds of the color material dispersion liquid, the photosensitive colored resin composition can be suitably used without setting the content ratio to be the same as that of the photosensitive colored resin composition described later.

The average primary particle size of the color material used in the second aspect of the present invention and the average dispersed particle size of the color material in the color material dispersion may be the same as those described for the color material items in the color material dispersion of the first aspect of the present invention, and therefore, the description thereof will be omitted.

In the color material dispersion liquid according to the second aspect of the present invention, the content of the color material may be the same as that described for the color material items in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof will be omitted.

< dispersant >

In a second aspect of the present invention, a polymer having a constituent unit represented by the above general formula (I) is used as a dispersant. The constituent unit represented by the general formula (I) has basicity and functions as an adsorption site for the color material.

In the color material dispersion liquid of the second aspect of the present invention, the polymer having the constitutional unit represented by the general formula (I) is used, whereby the adsorption performance for the color material is improved, and the dispersibility and dispersion stability of the color material are improved.

The constituent unit represented by the general formula (I) can be the same as those described in the item of the dispersant in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof is omitted here.

In the polymer having the constitutional unit represented by the general formula (I), from the viewpoint of further improving the color material adsorption property, the color material dispersion stability, and the solvent re-solubility in the salt-forming site, it is preferable that at least a part of the nitrogen site at the end of the constitutional unit represented by the general formula (I) forms a salt with 1 or more compounds selected from the group consisting of the compounds represented by the general formulae (1) to (3).

The 1 or more compounds selected from the group consisting of the following general formulae (1) to (3) may be the same as those described in the above description of the salt-type block copolymer of the dispersant in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof is omitted here.

[ chemical formula 11]

(the symbols in the general formulae (1) to (3) are as defined above.)

In the dispersant used in the second aspect of the present invention, the content of 1 or more compounds selected from the group consisting of the above general formulae (1) to (3) in the polymer having a constituent unit represented by the general formula (I) is the same as that described in the above description of the salt-type block copolymer of the dispersant in the color material dispersion liquid of the first aspect of the present invention, and therefore, the description thereof is omitted here.

The polymer having a constituent unit represented by the general formula (I) more preferably contains a site having solvent affinity from the viewpoint of improving dispersibility. The solvent affinity site is preferably selected from among monomers having an ethylenically unsaturated bond, which are polymerizable with a monomer derived from the constituent unit represented by the general formula (I), so as to have solvent affinity, as appropriate depending on the solvent. As a standard, it is preferable to introduce a solvent affinity site into a solvent used in combination so that the solubility of the polymer at 23 ℃ is 20(g/100g solvent) or more.

The polymer having a constituent unit represented by the general formula (I) used in the second aspect of the present invention is preferably a block copolymer or a graft copolymer, and particularly preferably a block copolymer, from the viewpoint of improving dispersibility and dispersion stability of the color material and heat resistance of the resin composition and forming a colored layer having high brightness and high contrast. The particularly preferred block copolymer will be described in detail below.

[ Block copolymer ]

When a block containing a constituent unit represented by the above general formula (I) is used as the a block, the a block has basicity in the constituent unit represented by the above general formula (I) and functions as an adsorption site for the color material. In addition, when at least a part of the nitrogen sites at the ends of the constituent unit represented by the general formula (I) forms a salt with 1 or more compounds selected from the group consisting of the following general formulae (1) to (3), the salt-forming portion functions as an adsorption site stronger for a color material. On the other hand, the B block not containing the constituent unit represented by the general formula (I) functions as a block having solvent affinity. Therefore, the block copolymer used in the present invention shares the functions of the a block adsorbed to the color material and the B block having solvent affinity, and thus functions as a color material dispersant.

The dispersant used in the second aspect of the present invention is a block copolymer having a constituent unit represented by the above general formula (I), and the amine value of the block copolymer is preferably 40mgKOH/g or more and 130mgKOH/g or less from the viewpoint of improving the dispersibility and dispersion stability of c.i. pigment green 59.

The lower limit of the dispersant used in the second aspect of the present invention is preferably 50mgKOH/g or more, and more preferably 60mgKOH/g or more, from the viewpoint of dispersibility of the color material and dispersion stability. The upper limit is preferably not more than 120 mgKOH/g. When the amount is not less than the lower limit, the dispersion stability is more excellent. When the content is not more than the upper limit, the compatibility with other components is excellent and the solvent re-solubility is good.

The amine value in the case of a salt-type block copolymer is smaller in a portion where only a salt is formed than in the case of a block copolymer before salt formation. However, since the salt-forming site is the same as or more strongly bonded to the terminal nitrogen site corresponding to the amino group, the dispersibility of the color material or the dispersion stability of the color material tends to be improved by salt formation. In addition, the salt-forming site is too much, as with the amino group, and adversely affects the solvent re-solubility. Therefore, in the present invention, the amine value of the block copolymer before the salt formation can be used as an index for improving the dispersion stability of the color material and the solvent re-solubility. The amine value of the resulting salt-type block copolymer (P2) is preferably from 0mgKOH/g to 130mgKOH/g, more preferably from 0mgKOH/g to 120 mgKOH/g.

{ A Block }

The a block is a block containing the constituent unit represented by the above general formula (I), and the constituent unit represented by the above general formula (I) is as described above, and therefore, the description thereof is omitted here.

The constituent unit represented by the general formula (I) may be composed of 1 species or may contain 2 or more species as long as it functions as a color material adsorption site.

The a block may have a constituent unit other than the constituent unit represented by the general formula (I) within the range to achieve the object of the present invention, and may be contained as long as it is a constituent unit copolymerizable with the constituent unit represented by the general formula (I). For example, the basic block portion may contain a structural unit other than the structural unit represented by the general formula (I), and specific examples thereof include a structural unit represented by the general formula (II) described below.

The content ratio of the constituent unit represented by the general formula (I) in the A block in the block copolymer before salt formation is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, most preferably 100% by mass, based on the total mass of all the constituent units of the A block. This is because the higher the proportion of the constituent unit represented by the general formula (I), the higher the adsorption force to the color material, and the better the dispersibility and dispersion stability of the block copolymer. The content ratio of the above-mentioned constituent units is calculated from the packing mass at the time of synthesizing an a block having the constituent unit represented by the general formula (I).

In the block copolymer before salt formation, the content ratio of the constituent unit represented by the general formula (I) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of all the constituent units of the block copolymer, from the viewpoint of improving dispersibility and dispersion stability. The content ratio of each constituent unit in the block copolymer is calculated from the packing quality at the time of synthesizing the block copolymer before salt formation.

{ B Block }

The B block is a block not containing the constituent unit represented by the above general formula (I). The B block is preferably selected from monomers having an unsaturated double bond copolymerizable with the monomer from which the constituent unit represented by the general formula (I) is derived, and is used as appropriate depending on the solvent so as to have solventropic properties. As a standard, it is preferable to introduce the B block so that the copolymer has a solubility at 23 ℃ of 20 or more (g/100g solvent) relative to the solvent used in combination.

The constituent unit constituting the B block includes a monomer having an unsaturated double bond copolymerizable with a monomer derived from the constituent unit represented by the general formula (I), and among them, the constituent unit represented by the following general formula (II) is preferable.

The constituent unit represented by the following general formula (II) may be the same as those described in the item of the dispersant in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof is omitted here.

[ chemical formula 12]

(the symbols in the general formula (II) are as defined above.)

The number of the constituent units constituting the B block is not particularly limited, and is preferably 10 to 300, more preferably 10 to 100, and still more preferably 10 to 70 from the viewpoint of effectively acting the solvent affinity site and the colorant adsorption site to improve the dispersibility of the colorant.

The content ratio of the constituent unit represented by the general formula (II) in the B block of the block copolymer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on the total mass of all the constituent units of the B block, from the viewpoint of improving the solvent affinity and the color material dispersibility. The content ratio of the above-mentioned constituent units is calculated from the packing mass at the time of synthesizing the B block.

In the block copolymer before salt formation, the content ratio of the constituent unit represented by the general formula (II) is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total mass of all the constituent units of the block copolymer, from the viewpoint of improving dispersibility of the color material and dispersion stability. The content ratio of the above-mentioned constituent units is calculated from the packing quality at the time of synthesizing the block copolymer before salt formation.

The B block may be constituted of 1 kind of constituent unit selected as appropriate so as to function as a solvophilic site, and the constituent unit represented by the above general formula (II) may be constituted of 2 or more kinds of constituent units. The 2 or more kinds of constituent units contained in the B block may be arranged randomly in the block.

The dispersant is preferably used from the viewpoint of being capable of providing a colored material with excellent dispersion stability, having an excellent effect of suppressing the generation of development residues, having excellent solvent re-solubility, and further having high development adhesion when used as a colored resin composition; the dispersant is at least 1 of the following block copolymer (P1) and the following salt-type block copolymer (P2);

p1: a block copolymer having an A block containing a constituent unit represented by the above general formula (I) and a B block containing a constituent unit derived from a carboxyl group-containing monomer;

p2: a salt-type block copolymer in which at least a part of the nitrogen sites at the ends of the constituent units represented by the general formula (I) of the block copolymer and 1 or more compounds selected from the group consisting of the compounds represented by the general formulae (1) to (3) form a salt;

the dispersant has an acid value of 1mgKOH/g or more and 18mgKOH/g or less, and a glass transition temperature of 30 ℃ or more.

When the concentration of the coloring material is increased and the content of the dispersant is increased, the binder amount is relatively decreased, and therefore, the colored resin layer is easily peeled off from the base substrate during development. The dispersant contains a B block containing a constituent unit derived from a carboxyl group-containing monomer, and has the above-mentioned specific acid value and glass transition temperature, whereby development adhesion is improved. It is presumed that when the acid value is too high, although the developability is excellent, the polarity is too high, and conversely, peeling is likely to occur during development.

Such a dispersant may be the same as that described in the above-mentioned dispersant used in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof is omitted here.

In the color material dispersion liquid according to the second aspect of the present invention, at least 1 of the polymers having the structural unit represented by the above general formula (I) is used as the dispersant, and the content thereof is appropriately selected depending on the kind of the color material to be used, the solid content concentration in the photosensitive colored resin composition for a color filter to be described later, and the like.

In the color material dispersion liquid according to the second aspect of the present invention, the content of the dispersant may be the same as that described above for the dispersant used in the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof is omitted here.

The solvent used in the color material dispersion liquid of the second aspect of the present invention, the content thereof, other components that can be blended as needed, and the method for producing the color material dispersion liquid may be the same as those described above for the color material dispersion liquid of the first aspect of the present invention, and therefore, the description thereof will be omitted.

The color material dispersion liquid according to the second aspect of the present invention is used as a pre-prepared product for preparing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention described later. That is, the color material dispersion is a color material dispersion prepared in advance in the preparation of a photosensitive colored resin composition for a color filter, which will be described later, and having a high ratio of (mass of color material component in the composition)/(mass of solid component other than color material component in the composition). Specifically, the ratio of (mass of color material component in the composition)/(mass of solid component other than color material component in the composition) is usually 1.0 or more. The photosensitive colored resin composition for a color filter of the second aspect of the present invention having excellent dispersibility can be prepared by mixing the color material dispersion of the second aspect of the present invention with the respective components described below.

II-2. the photosensitive colored resin composition for a color filter of the second aspect of the invention

(i) First embodiment of the second aspect of the present invention

The photosensitive colored resin composition for a color filter of the second aspect of the present invention is a photosensitive colored resin composition for a color filter containing a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,

the color material contains c.i. pigment green 59;

the dispersant is a polymer having a constituent unit represented by the general formula (I).

In the photosensitive colored resin composition for a color filter according to the first aspect of the present invention, the color material contains c.i. pigment green 59, whereby the green region having a high color density can be formed, and a colored layer having high brightness and high contrast can be formed. The photosensitive colored resin composition for a color filter according to the first embodiment of the second aspect of the present invention can form a colored layer having excellent solvent re-solubility, high brightness, high contrast, and excellent color reproducibility by the same action as described in the color material dispersion according to the first embodiment of the second aspect of the present invention.

(ii) Second aspect of the present invention

A photosensitive colored resin composition for a color filter of a second aspect of the present invention is a photosensitive colored resin composition for a color filter containing a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,

the color material contains C.I. pigment green 59 and yellow color material;

the dispersant includes a polymer having a constituent unit represented by the following general formula (I).

In the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, since the color material contains c.i. pigment green 59 and a yellow color material and a polymer having a constituent unit represented by general formula (I) is used in combination as a dispersant, a colored layer having excellent color material dispersion stability, suppressed occurrence of display failure, high luminance, and excellent color reproducibility can be formed by the same action as described in the color material dispersion liquid according to the second embodiment of the present invention.

(iii) Third aspect of the second aspect of the present invention

A photosensitive colored resin composition for a color filter according to a third aspect of the present invention is a photosensitive colored resin composition for a color filter comprising a coloring material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, since the color material contains c.i. pigment green 59, a blue color material and the specific yellow color material, and a polymer having a constituent unit represented by the general formula (I) is used in combination as a dispersant, a colored layer having excellent color material dispersion stability, high luminance and excellent color reproducibility can be formed by the same action as described in the color material dispersion liquid according to the third embodiment of the second aspect of the present invention, while suppressing the occurrence of display failure.

The photosensitive colored resin composition for a color filter of the second aspect of the present invention contains at least a coloring material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and may further contain other components within a range not impairing the effects of the present invention. The respective components contained in the photosensitive colored resin composition for a color filter according to the second aspect of the present invention will be described below, but the c.i. pigment green 59 and the dispersant, which are essential components in the color material, are the same as those described above in the dispersion liquid of the color material according to the second aspect of the present invention, and therefore, the description thereof will be omitted. The solvent may be the same as that described above for the color material dispersion liquid according to the first aspect of the present invention, and therefore, the description thereof is omitted here. The alkali-soluble resin, the polyfunctional monomer, the photoinitiator, and other components may be the same as those described above for the photosensitive colored resin composition for a color filter according to the first aspect of the present invention, and therefore, the description thereof will be omitted.

< color Material >

The color material in the photosensitive colored resin composition for a color filter according to the second aspect of the present invention contains c.i. pigment green 59 as an essential component, but other color materials may be used in combination in order to adjust the color tone.

The color filter is not particularly limited as long as it can emit a desired color when a colored layer of the color filter is formed, and various organic pigments, inorganic pigments, and dispersible dyes may be used alone or in combination of 2 or more. Among them, organic pigments are preferably used because they have high color-developing properties and high heat resistance. Examples of The organic Pigment include compounds classified as pigments (Pigment) in The color index (C.I.; issued by The Society of dyers and Colourists Co., Ltd.), and specifically, pigments having a color index (C.I.) number attached thereto as described below.

As another color material, a color material other than PG59 as exemplified in the color material items of the color material dispersion liquid according to the first aspect of the present invention can be used in combination as another color material. Among them, a yellow color material, another green color material, and a blue color material are preferably used.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, it is preferable to further use a yellow color material in combination with PG59, from the viewpoint of suppressing the occurrence of display defects in green pixels and forming a colored layer having high luminance and excellent color reproducibility (the second embodiment of the second aspect of the present invention). The yellow color material used in the second embodiment of the second aspect of the present invention may be the same as that described in the color material dispersion liquid of the second embodiment of the second aspect of the present invention. As the other color material used in the second embodiment of the second aspect of the present invention, other green color material, blue color material, and orange color material are preferably used.

Among them, in the photosensitive colored resin composition for a color filter according to the second embodiment of the second aspect of the present invention, it is preferable that at least 1 of PG58 and PG7 is contained in addition to PG 59. Among them, PG58 is preferably contained in addition to PG59 in order to achieve a target chromaticity, suppress display defects, and form a green pixel with high luminance. When PG59 and PG58 are used in combination, color reproducibility can be increased, the P/V ratio can be decreased, and luminance can be improved as compared with PG58 alone. On the other hand, among them, from the viewpoint of achieving a target chromaticity, suppressing display defects, further reducing the P/V ratio, improving platemaking properties such as development resistance, it is preferable to contain PG7 in addition to PG 59. In addition, from the viewpoint of achieving a target chromaticity, suppressing display defects, and improving the balance between luminance and platemaking property due to the reduction in P/V ratio, it is preferable to include PG58 and PG7 in addition to PG 59.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the second aspect of the present invention, the content ratio of PG59 to the entire color material can be appropriately adjusted depending on the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects and enhancing color reproducibility to improve luminance, PG59 is preferably contained in an amount of 5 to 95 mass%, more preferably 10 to 90 mass%, and still more preferably 20 to 80 mass% with respect to the entire color material containing PG 59.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the second aspect of the present invention, the content ratio of the yellow color material to PG59 may be appropriately adjusted depending on the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects and increasing color reproducibility and brightness, it is preferable to contain 10 to 900 parts by mass, more preferably 20 to 400 parts by mass of the yellow color material with respect to 100 parts by mass of PG 59.

In the photosensitive colored resin composition for a color filter of the second aspect of the present invention, the yellow color material is appropriately selected and used alone in 1 kind or in combination with 2 or more kinds, and among them, 1 or more kinds selected from the group consisting of PY138, PY139, PY185, PY150 and their derivative pigments are preferable from the viewpoint of easily realizing a colored layer which suppresses the occurrence of display defects and has high luminance and high contrast and excellent color reproducibility.

In the second embodiment of the second aspect of the present invention, the PY150 and the derivative pigment thereof are preferably used in the case where the pigment represents a chromaticity region where y is 0.550 to 0.610 and x is 0.205 to 0.324, and the P/V ratio is preferably more easily decreased in the chromaticity region.

PY138 is preferably used to realize high luminance in a chromaticity region where y is 0.550 to 0.610 and x is 0.205 to 0.324, and more preferably used to realize high luminance in a chromaticity region where x is 0.246 to 0.324.

PY185 is suitable for increasing the color gamut, and preferably represents a chromaticity region where x is 0.205 to 0.324 even when y is 0.610 to 0.626, and more preferably represents a chromaticity region where y is 0.659.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, when at least 1 of the pigments of PY150 and its derivatives and PY138 are used in combination, the total amount of the at least 1 of the pigments of PY150 and its derivatives and PY138 are preferably 5: 95 to 95: 5, which is appropriately adjusted depending on the desired chromaticity, brightness, and film thickness. Among them, the ratio of the total amount of at least 1 of the PY150 and the derivative pigment thereof to PY138 is more preferably 10: 90 to 90: 10 from the viewpoint of the lightness and the P/V ratio, and is still more preferably 20: 80 to 80: 20 from the viewpoint of the lightness and the P/V ratio.

In the case where a green color material other than PG59 is further contained in the photosensitive colored resin composition for a color filter according to the second embodiment of the second aspect of the present invention, the content ratio of the green color material containing PG59 to the entire color material can be appropriately adjusted depending on the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects and increasing color reproducibility to increase luminance, the green color material containing PG59 is preferably contained by 10 to 90 mass%, more preferably 20 to 80 mass%, based on the entire color material.

The content ratio of the yellow color material to the green color material containing PG59 can be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects and increasing color reproducibility to increase luminance, the yellow color material is preferably contained in an amount of 10 to 900 parts by mass, more preferably 20 to 400 parts by mass, based on 100 parts by mass of the green color material containing PG 59.

In addition, in the case where at least one of PG58 and PG7 is further contained in the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, it is preferable that at least 1 of PG58 and PG7 is contained by 5 to 50% by mass with respect to the whole of the green color material containing PG59, and in particular, it is more preferable that it is contained by 5 to 40% by mass from the viewpoint of the ratio of the display defect to the luminance to the P/V, and still more preferable that it is contained by 5 to 30% by mass from the viewpoint of the ratio of the luminance to the P/V.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, the color material may further contain another color material other than the green color material and the yellow color material within a range not impairing the effects of the present invention, and the total content of the green color material containing PG59 and the yellow color material is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the entire color materials.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, a blue color material and a yellow color material are combined as the color materials in PG 59; the yellow color material is (Y1) containing at least 1 kind of yellow color material of c.i. pigment yellow 185, or (Y2) containing, as an essential component, c.i. pigment yellow 139, and further containing at least 1 or more kinds of at least 2 kinds of yellow color materials selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150, and a derivative pigment thereof (third embodiment of the second aspect of the present invention). The blue color material and the specific yellow color material used in the third embodiment of the second aspect of the present invention may be the same as those described in the color material dispersion liquid of the third embodiment of the second aspect of the present invention. As the other color material used in the third embodiment of the second aspect of the present invention, it is preferable to use other green color material and orange color material.

Among them, the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention preferably contains PG7 from the viewpoints of achieving a target chromaticity, suppressing display defects, further reducing the P/V ratio, suppressing development residues, and improving development adhesion and plate-making properties.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the content ratio of PG59 to the entire color material can be appropriately adjusted depending on the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects and enhancing color reproducibility to improve luminance, PG59 is preferably contained in an amount of 5 to 80 mass%, more preferably 10 to 70 mass%, and still more preferably 10 to 60 mass% with respect to the entire color material containing PG 59.

In the photosensitive colored resin composition for a color filter of the third embodiment of the second aspect of the present invention, the content ratio of the blue coloring material to PG59 may be appropriately adjusted depending on the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects and increasing color reproducibility and brightness, the blue color material is preferably contained in an amount of 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, based on 100 parts by mass of PG 59.

The blue color material is preferably contained in an amount of 3 to 60% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass based on the total amount of the color materials.

In the photosensitive colored resin composition for a color filter of the third embodiment of the second aspect of the present invention, the content ratio of the yellow color material to PG59 may be appropriately adjusted depending on the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects and increasing color reproducibility and brightness, the yellow color material is preferably contained in an amount of 10 to 800 parts by mass, more preferably 20 to 600 parts by mass, based on 100 parts by mass of PG 59.

The yellow color material is preferably contained in an amount of 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 70% by mass, based on the total amount of the color materials.

In the photosensitive colored resin composition for a color filter of the third embodiment of the second aspect of the present invention, the content ratio of the yellow color material to the blue color material may be appropriately adjusted depending on the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects and increasing color reproducibility and brightness, the yellow color material is preferably contained in an amount of 10 to 800 parts by mass, more preferably 20 to 600 parts by mass, based on 100 parts by mass of the blue color material.

In the photosensitive colored resin composition for a color filter of the third embodiment of the second aspect of the present invention, when (Y1) contains at least 1 yellow color material of c.i. pigment yellow 185, the content of PY185 based on the total amount of the yellow color materials is preferably 10 to 100% by mass, and more preferably 20 to 100% by mass. PY185 has a strong coloring power, and even if it is contained in an amount of about 10% by mass based on the total amount of the yellow coloring material, it has an effect of lowering the P/V ratio.

When PY139 is contained in addition to PY185 in (Y1), the content of PY139 is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, based on the total amount of the yellow color material, as (Y1).

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, when (Y2) contains c.i. pigment yellow 139 as an essential component and further contains 1 or more kinds of at least 2 kinds of yellow color materials selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150 and a pigment derived therefrom, the content of PY139 is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, based on the total amount of the yellow color materials. The content of 1 or more selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 150, and derivatives thereof is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, based on the total amount of the yellow color material.

In the above (Y2), in view of suppressing the occurrence of display defects and easily realizing a colored layer having high brightness and high contrast, it is preferable that PY139 be an essential component and that at least 2 yellow color materials selected from the group consisting of PY150 and a pigment derived from the PY150 be contained. In addition, as (Y2), when a combination of at least 2 yellow color materials containing PY139 and 1 or more selected from the group consisting of PY150 and pigments derived therefrom, and the PG59 and blue color materials is used, it is preferable from the viewpoint of further reducing the P/V ratio, suppressing development residue, and improving development adhesion and platemaking properties.

In the above combination, at least 2 kinds of yellow color materials containing PY139 as an essential component and further containing a derivative pigment of PY150 containing a nickel-containing complex are preferable from the viewpoint of improving the luminance and easily lowering the P/V ratio.

In the case where PY139 is combined with 1 or more selected from the group consisting of PY150 and a pigment derived therefrom, (Y2) is preferably contained in an amount of 1 or more selected from the group consisting of PY150 and a pigment derived therefrom in excess of the content of PY139, more preferably 150 to 700 parts by mass, and still more preferably 200 to 600 parts by mass, based on 100 parts by mass of PY139, from the viewpoint of easily realizing a colored layer having high brightness and high contrast.

In the photosensitive colored resin composition for a color filter of the third embodiment of the second aspect of the present invention, the specific yellow color material is appropriately selected and may be used alone in 1 kind or in a mixture of 2 or more kinds.

In the second aspect of the present invention, PY185 is suitable for increasing the color reproduction range, and is preferably used when the chromaticity range is represented by y of 0.610 to 0.720 and x of 0.140 to 0.230, and even when y of 0.720 to 0.750, is preferably used when the chromaticity range is represented by x of 0.140 to 0.210.

Further, PY139 is preferably used for a chromaticity region where y is 0.570 to 0.710 and x is 0.180 to 0.265.

In the case where a green color material other than PG59 is further contained in the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the content ratio of the green color material containing PG59 to the entire color material can be appropriately adjusted depending on the desired chromaticity, and is not particularly limited.

Even when a green color material other than PG59 is further contained, the content ratio of the green color material containing PG59 to the entire color material, the content ratio of the blue color material to the green color material containing PG59, the content ratio of the blue color material to the entire color material, the content ratio of the yellow color material to the green color material containing PG59, and the content ratio of the yellow color material to the entire color material are preferably the same as the content ratio of PG59 to the entire color material, the content ratio of the blue color material to PG59, the content ratio of the blue color material to the entire color material, the content ratio of the yellow color material to PG59, and the content ratio of the yellow color material to the entire color material, respectively.

In addition, in the case where PG7 is further contained in the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, PG7 is preferably contained in an amount of 5 to 50% by mass, more preferably 5 to 45% by mass, based on the total amount of the green color material containing PG59, from the viewpoint of the display defect and the luminance and the above P/V ratio.

In the photosensitive colored resin composition for a color filter of the third embodiment of the second aspect of the present invention, the color material may further contain another color material other than the green color material, the blue color material and the yellow color material within a range not to impair the effects of the present invention, and the total content of the green color material, the blue color material and the specific yellow color material containing PG59 is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the entire color materials.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, the P/V ratio ((mass of color material component in composition)/(mass of solid component other than color material component in composition)) is preferably 0.1 or more, more preferably 0.2 or more, from the viewpoint of deaeration and heat shrinkage; on the other hand, from the viewpoint of exhibiting poor performance and excellent manufacturing convenience, that is, excellent solvent resolubility, development residue, development adhesion, development resistance, water bleeding inhibition effect, and the like, it is preferably 0.7 or less, more preferably 0.6 or less, and still more preferably 0.5 or less.

< cured film of photosensitive colored resin composition for color Filter >

In the photosensitive colored resin composition for a color filter according to the second embodiment of the second aspect of the present invention, it is preferable that a cured film having chromaticity coordinates in the XYZ colorimetric system of JIS Z8701 measured with a C light source of x 0.180 to 0.330 and y 0.500 to 0.750 be formed.

Among them, from the viewpoint of improving color reproducibility, the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention is preferably capable of forming a cured film having chromaticity coordinates x of 0.188 to 0.324 and y of 0.550 to 0.750 in an XYZ color system of JIS Z8701 measured using a C light source, more preferably capable of forming a cured film having chromaticity coordinates x of 0.200 to 0.324 and y of 0.570 to 0.750, and still more preferably capable of forming a cured film having chromaticity coordinates x of 0.205 to 0.324 and y of 0.580 to 0.750.

In the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, the film thickness is 2.8 μm or less, and in the chromaticity coordinates in the XYZ color system of JIS Z8701 where color measurement is performed using a C light source for a single pixel, a chromaticity space in which x is 0.200 to 0.300, Y is 0.570 to 0.750, and stimulus value Y is 37 or less is preferably represented, and a chromaticity space in which x is 0.200 to 0.300, Y is 0.570 to 0.750, and stimulus value Y is 40 or less is more preferably represented.

The total content of the color materials is 20 to 45 mass% based on the total solid content of the photosensitive colored resin composition for a color filter, as a good blending ratio or combination of chromaticity spaces which can represent a range of 37. ltoreq. Y; the ratio (G: Y) of the green color material (G) and the yellow color material (Y) containing PG59 is preferably 80: 20 to 20: 80. In the above, the content of PG59 in the green color material (G) containing PG59 is more preferably 30% by mass or more. The cured film herein has a film thickness after the photosensitive colored resin composition for a color filter is applied, dried, exposed to light, cured, and post-baked in a dust-free oven at 230 ℃ for 30 minutes.

The photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention is preferably capable of forming a cured film having chromaticity coordinates x of 0.140 to 0.330 and y of 0.500 to 0.750 in an XYZ color system of JIS Z8701, which is measured using a C light source.

Among them, from the viewpoint of improving color reproducibility, the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention is preferably capable of forming a cured film having chromaticity coordinates x of 0.140 to 0.280 and y of 0.570 to 0.730, more preferably capable of forming a cured film having chromaticity coordinates x of 0.140 to 0.265 and y of 0.610 to 0.720, and still more preferably capable of forming a cured film having chromaticity coordinates x of 0.180 to 0.230 and y of 0.690 to 0.710 in the XYZ color system of JIS Z8701 measured using a C light source.

In the cured film of the photosensitive colored resin composition for a color filter according to the third aspect of the present invention, the film thickness is 2.8 μm or less, and in the chromaticity coordinates in the XYZ color system of JIS Z8701 where color measurement is performed using a C light source for a single pixel, a chromaticity space in which x is 0.140 to 0.265, Y is 0.570 to 0.720, and stimulus value Y is 16 or less is preferably displayable, and a chromaticity space in which x is 0.140 to 0.230, Y is 0.610 to 0.720, and stimulus value Y is 18 or less is more preferably displayable. The cured film herein has a film thickness obtained by applying and drying the photosensitive colored resin composition for a color filter, exposing the composition to light, curing the polyfunctional monomer, and post-baking the cured film in a dust-free oven at 230 ℃ for 30 minutes.

As a good blending ratio or combination of chromaticity spaces in the XYZ color system of JIS Z8701, in which the film thickness is 2.8 μm or less and the color is measured with a single pixel using a C light source, in which x is 0.140 to 0.230, Y is 0.610 to 0.720, and the stimulus value Y is 18. ltoreq. Y, it is preferable to use (Y1) as the yellow color material; preferably, the pigment composition contains 10 to 70 mass% of a green color material, 5 to 50 mass% of a blue color material and 10 to 70 mass% of a yellow color material, based on the total amount of the color materials, of C.I. pigment green 59; more preferably, the c.i. pigment green 59 is contained in an amount of 15 to 60 mass% in terms of green color material, 10 to 40 mass% in terms of blue color material, and 20 to 60 mass% in terms of yellow color material, based on the total amount of the color materials.

In addition, as a good blending ratio or combination of chromaticity space which can represent the ranges of x 0.180 to 0.265, Y0.570 to 0.710 and stimulus value Y16 ≦ Y, it is preferable to use the above (Y2) as a yellow color material; preferably, the pigment composition contains 10 to 70 mass% of a green color material, 5 to 50 mass% of a blue color material and 10 to 70 mass% of a yellow color material, based on the total amount of the color materials, of C.I. pigment green 59; the amount of the green color material, the blue color material and the yellow color material containing C.I. pigment green 59 is preferably 15 to 60 mass%, 10 to 40 mass% and 20 to 60 mass%, respectively, based on the total amount of the color materials.

The method for producing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention is not particularly limited, and can be obtained, for example, by adding an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and, if necessary, other components to the color material dispersion according to the second aspect of the present invention, and mixing them by a known mixing means. Alternatively, in the case where a different color material from PG59 is contained as in the second or third embodiment, a color material dispersion liquid of PG59, a color material dispersion liquid of a yellow color material, and further, if necessary, a color material dispersion liquid of another color material are prepared, respectively, using the above-described dispersant, and the color material dispersion liquid containing PG59, the color material dispersion liquid containing a yellow color material, and further, if necessary, a color material dispersion liquid of another color material, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and if necessary, other components are mixed by using a known mixing means, whereby a colored resin composition for a color filter can be obtained.

II-3. color Filter of the second aspect of the invention

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

In the color filter according to the second aspect of the present invention, at least one of the colored layers has a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, and thus a color filter having high brightness, high contrast, and excellent color reproducibility can be obtained.

The color filter according to the second aspect of the present invention may have the same structure as that described for the color filter according to the first aspect of the present invention, as long as it has a colored layer formed by curing the photosensitive colored resin composition for a color filter according to the second aspect of the present invention, and therefore, the description thereof will be omitted.

II-4, 5. liquid crystal display device and organic light emitting display device of the second aspect of the present invention

A liquid crystal display device according to a second aspect of the present invention is characterized by having the color filter according to the second aspect of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

An organic light emitting display device of a second aspect of the present invention is characterized by having: the color filter and the organic light-emitting device according to the second aspect of the present invention are described above.

In the second aspect of the present invention, by using the second color filter, a liquid crystal display device and an organic light emitting display device having high luminance and excellent color reproducibility can be provided.

The liquid crystal display device and the organic light emitting display device according to the second aspect of the present invention may have the same configurations as those described in the liquid crystal display device and the organic light emitting display device according to the first aspect of the present invention, as long as the color filter according to the second aspect of the present invention is provided, and therefore, the descriptions thereof are omitted.

Examples

The following examples are presented to illustrate the present invention in detail. The present invention is not limited by these descriptions.

The acid value of the block copolymer before salt formation and the acid value of the salt-type block copolymer salified with the compound represented by the above general formula (2) were determined by the methods described in JIS K0070.

The amine value of the block copolymer before salt formation and the amine value of the salt-type block copolymer salified with the compound represented by the above general formula (2) are determined by the methods described in JIS K7237.

The glass transition temperature (Tg) of the block copolymer before and after salt formation was measured by Differential Scanning Calorimetry (DSC) (exidsc 7020, manufactured by SII Nano Technology) using the method described in JIS K7121.

The weight average molecular weight (Mw) of the block copolymer before salt formation is determined by GPC (gel permeation chromatography) as a standard polystyrene conversion value according to the measurement method of the present invention.

The glass transition temperatures (Tg) of the block copolymers A-1 and A-26 of the following synthetic examples and the block copolymers A-22 and A-24 of the comparative examples were determined by the following formula. As a result, it was found that the temperature of the block copolymer A-1 was 37 ℃ (DSC measurement of 38 ℃), the temperature of the block copolymer A-26 was 64 ℃ (DSC measurement of 66 ℃), the temperature of the block copolymer A-22 was 0 ℃ (DSC measurement of 2 ℃), and the temperature of the block copolymer A-24 was 20 ℃ (DSC measurement of 20 ℃), which are almost the same as the DSC measurement.

1/Tg＝∑(Xi/Tgi)

Here, the block copolymer is obtained by copolymerizing n monomer components from 1 to n. Xi is the weight fraction of the ith monomer (Σ Xi ═ 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the ith monomer. Where Σ is the sum of i and 1 to n. Note that the value of the homopolymer glass transition temperature (Tgi) of each monomer is a value obtained by using Polymer Handbook, 3rd Edition (j. brand, e.h. immergut, Wiley-Interscience, 1989). Specifically, the values (Tgi) of the homopolymer glass transition temperatures of the monomers used in the examples and comparative examples are shown below.

Methacrylic acid (MAA): 185 deg.C

2-hydroxyethyl methacrylate (HEMA): 55 deg.C

2-ethylhexyl methacrylate (EHMA): -10 deg.C

n-Butyl Methacrylate (BMA): 20 deg.C

Benzyl methacrylate (BzMA): 54 deg.C

Methyl Methacrylate (MMA): 105 ℃ C

Cyclohexyl methacrylate (CHMA): 83 deg.C

Dimethylaminoethyl methacrylate (DMMA): 18 deg.C

Dimethylaminopropyl methacrylamide (DMAPMA): 96 deg.C

Methoxypolyethylene glycol monomethacrylate (trade name: PME-100, manufactured by Nichikoku K.K., BLEMMER-PME-100, ethyleneoxy repeat number ═ 2): -26 deg.C

Methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by Nichikoku K.K., BLEMMER-PME-200, ethyleneoxy repeat number ═ 4): -59 deg.C

2-hydroxy-3-phenoxypropyl acrylate (HPhPA) (trade name: M-600A, manufactured by Kyoeisha chemical Co., Ltd.): 17 deg.C

Example I series: first aspect of the invention

(Synthesis example 1: production of Block copolymer A-1)

In a 500mL 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 THF and 0.6 part by mass of lithium chloride were charged to sufficiently replace nitrogen. After the reaction flask was cooled to-60 ℃, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 0.37 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.6 parts by mass of 2-ethylhexyl methacrylate (EHMA), 15.4 parts by mass of n-Butyl Methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA) and 29.3 parts by mass of Methyl Methacrylate (MMA) as monomers for the B block were added dropwise over 60 minutes using an addition funnel. After 30 minutes, 27.0 parts by mass of dimethylaminoethyl methacrylate (DMMA) as a monomer for a block was added dropwise over 20 minutes. After 30 minutes of the reaction, 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 a solution having a solid content of 30 mass%. 32.5 parts by mass of water was added, the temperature was raised to 100 ℃ to react for 7 hours, and the EEMA-derived constituent unit was deprotected to produce a methacrylic acid (MAA) -derived constituent unit. The obtained block copolymer PGMEA solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer A-1 (acid value 1mgKOH/g, Tg38 ℃ C.) containing an A block comprising a constituent unit represented by the general formula (I) and a B block containing a constituent unit derived from a carboxyl group-containing monomer and having solvophilicity. The thus-obtained block copolymer A-1 was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 7600. Further, the amine value was 96 mgKOH/g.

(Synthesis examples 2 to 3: Synthesis of Block copolymers A-2 to A-3)

In Synthesis example 1, block copolymers A-2 to A-3 were synthesized in the same manner as in Synthesis example 1 except that the contents were changed to those shown in Table 1. In Synthesis example 2, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA); in Synthesis example 3, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. The acid value, Tg and amine value of the obtained block copolymer are shown in Table 1.

Synthesis example 4 Synthesis of salt-type Block copolymer A-4

First, a block copolymer A-2 was synthesized in the same manner as in Synthesis example 2 (the block copolymer before salt formation of the salt-type block copolymer A-4 was the same as the block copolymer A-2).

In a 100mL round-bottomed flask, 10.0 parts by mass of block copolymer A-2 was dissolved in 41.93 parts by mass of PGMEA, 0.48 parts by mass of phenylphosphonic acid (manufactured by Tokyo chemical conversion) as a compound represented by the above general formula (3) (0.20 mol per 1mol of DMMA unit of block copolymer A-2 relative to the compound represented by the above general formula (3)) was added, and the mixture was stirred at a reaction temperature of 30 ℃ for 20 hours to obtain a salt-type block copolymer A-4 solution having a solid content of 20% by mass. The acid value of the block copolymer after salt formation was the same as that of the block copolymer A-2, and the amine value after salt formation was calculated specifically as follows.

An NMR sample tube was charged with 1g of a solution containing 9 parts by mass of a salt-type block copolymer A-4 (solid matter after reprecipitation) and 91 parts by mass of chloroform-D1 NMR, and a 13C-NMR spectrum was measured at room temperature and a cumulative frequency of 10000 times using a nuclear magnetic resonance apparatus (FT NMR, JNM-AL400, manufactured by Japan). In the obtained spectral data, the ratio of the number of amino groups to the total number of amino groups to be salified was calculated from the ratio of the integrated values of the peak of carbon atoms adjacent to nitrogen atoms not salified and the peak of carbon atoms adjacent to nitrogen atoms to be salified at the terminal nitrogen site (amino group), and it was confirmed that there was no difference from the theoretical salt formation ratio (all phenylphosphonic acids formed salts with the terminal nitrogen site of DMMA of block copolymer a-2).

The amine value after salt formation was calculated as 76mgKOH/g by subtracting the amine value (19mgKOH/g) of 0.20 molar parts of DMMA units from the amine value before salt formation of 95 mgKOH/g. The Tg's of the block copolymers before and after salt formation are also shown in Table 1.

(Synthesis examples 5 to 10: Synthesis of salt-type Block copolymers A-5 to A-10)

Synthesis example 4 was repeated in the same manner as in Synthesis example 4 except that the salt-forming compound was changed to the compounds and amounts shown in Table 1 to obtain solutions of salt-type block copolymers A-5 to A-10.

In the salt-type block copolymers A-5 to A-10, the acid value, Tg and amine value of the block copolymer before salt formation, and the acid value, amine value and Tg of the salt-type block copolymer (after salt formation) are shown in Table 1.

In table 1, the amount of 1 or more compounds selected from the group consisting of the compounds represented by the general formulae (1) to (3) is represented by the number of moles of the compound per 1 mole of the nitrogen site (DMMA) of the constituent unit represented by the general formula (I).

(Synthesis examples 11 to 12: Synthesis of salt-type Block copolymers A-11 to A-12)

In Synthesis example 1, block copolymers A-11 to A-12 used in comparative examples were synthesized in the same manner as in Synthesis example 1 except that the contents were changed to those shown in Table 1. The acid value, Tg and amine value of the obtained block copolymer are shown in Table 1.

Synthesis example 13 production of Block copolymer A-13

In a 500mL 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 5.81 parts by mass of dimethylketene methyltrimethylacetal as an initiator were charged through the addition funnel, and nitrogen substitution was sufficiently performed. 0.5 part by mass of a 1mol/L acetonitrile solution of tetrabutylammonium o-chlorobenzoic acid as a catalyst was injected by a syringe, and 18.7 parts by mass of HEMA, 12.8 parts by mass of EHMA, 13.7 parts by mass of BMA, 9.5 parts by mass of BzMA9, and 19.5 parts by mass of MMA, which are monomers for B block, were added dropwise over 60 minutes using an addition funnel. The reaction flask was cooled with an ice bath to maintain the temperature below 40 ℃. After 1 hour, 25.8 parts by mass of DMMA as a monomer for a block was added dropwise over a period of 20 minutes. After 1 hour of the reaction, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer A-13(Tg37 ℃) containing an A block comprising the constitutional unit represented by the general formula (I) and a solvent-philic B block. The thus-obtained block copolymer A-13 was confirmed by GPC (gel permeation chromatography), and the weight-average molecular weight Mw was 7320. Further, the amine value was 92 mgKOH/g.

(Synthesis examples 14 to 17: Synthesis of salt-type Block copolymers A-14 to A-17)

Synthesis example 4 was repeated in the same manner as in Synthesis example 4 except that the block copolymer A-13 of Synthesis example 13 (the block copolymer before salt formation of the salt-type block copolymers A-14 to A-17 was the same as the block copolymer A-13) was used as the block copolymer before salt formation, and the compounds and amounts shown in Table 1 were changed as the salt-forming compounds to obtain salt-type block copolymers A-14 to A-17 solutions.

In the salt-type block copolymers A-14 to A-17, the acid value, Tg and amine value of the block copolymer before salt formation and the acid value, amine value and Tg of the salt-type block copolymer (after salt formation) are shown in Table 1.

(Synthesis examples 18 to 34: Synthesis of Block copolymers A-18 to A-34)

In Synthesis example 1, the block copolymers A-18 to A-34 used in examples or comparative examples were synthesized in the same manner as in Synthesis example 1 except that the contents shown in Table 2 or Table 3 were changed. The acid value, Tg and amine value of the obtained block copolymer are shown in Table 2 or Table 3.

(Synthesis examples 35 to 37: Synthesis of salt-type Block copolymers A-35 to A-37)

Synthesis example 4 was repeated in the same manner as in Synthesis example 4 except that the block copolymer A-33 of Synthesis example 33 (the block copolymer before salt formation of the salt-type block copolymers A-35 to A-37 was the same as the block copolymer A-33) was used as the block copolymer before salt formation, and the compounds and amounts shown in Table 3 were changed as the salt-forming compounds to obtain salt-type block copolymers A-35 to A-37 solutions.

In the salt-type block copolymers A-35 to A-37, the acid value, Tg and amine value of the block copolymer before salt formation and the acid value, amine value and Tg of the salt-type block copolymer (after salt formation) are shown in Table 3.

(Synthesis examples 38 to 40: Synthesis of Block copolymers A-38 to A-40)

The block copolymers A-38 to A-40 used in comparative examples were synthesized in the same manner as in Synthesis examples 1, 2 and 5(B-1, B-2 and B-5) of patent document 2. The acid value, Tg and amine value of the obtained block copolymer are shown in Table 4.

[ Table 1]

[ Table 2]

[ Table 3]

Table 3.

[ Table 4]

Table 4.

Synthesis example 41 (Synthesis of alkali-soluble resin A solution)

After charging 300 parts by mass of PGMEA in a polymerization vessel and raising the temperature to 100 ℃ 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), 6 parts by mass of PERBUTYL O (manufactured by nippon oil co., ltd.) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction was continued while maintaining 100 ℃ and 2 hours elapsed since the completion of the dropwise addition of the main chain-forming mixture, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor was added to stop the polymerization.

Subsequently, 20 parts by mass of Glycidyl Methacrylate (GMA) was added as an epoxy group-containing compound while blowing air, the temperature was raised to 110 ℃, and then 0.8 part by mass of triethylamine was added to conduct an addition reaction at 110 ℃ for 15 hours, thereby obtaining an alkali-soluble resin A solution (weight average molecular weight (Mw)8500, acid value 75mgKOH/g, solid content 40 mass%).

The weight average molecular weight was measured by Shodex GPC system-21H (Shodex GPC system-21H) using polystyrene as a standard substance and THF as an eluent. The acid value was measured in accordance with JIS K0070.

(example 1)

(1) Production of color Material Dispersion G-1

3.25 parts by mass of the block copolymer A-I of Synthesis example 1 as a dispersant, 11.7 parts by mass of C.I. pigment Green 58(PG58) as a coloring material, 1.3 parts by mass of C.I. pigment yellow 138(PY138), 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0mm were put in a mayonnaise bottle, and vibrated for 1 hour with a pigment vibrator (manufactured by Kubota Seiko Co., Ltd.) to preliminarily pulverize, followed by taking out the zirconia beads having a particle size of 2.0mm, adding 200 parts by mass of the zirconia beads having a particle size of 0.1mm, and dispersed for 4 hours in the same manner as the pigment vibrator to preliminarily pulverize to obtain a coloring material dispersion G-1.

(2) Production of photosensitive colored resin composition G-1 for color Filter

To the color material dispersion liquid G-111.40 parts by mass obtained in the above-mentioned (1), 0.64 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 0.60 parts by mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by TOYOBO SYNTHESIS CO., LTD.), 0.09 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name: IRGACURE907, (manufactured by TOYOBO SYNTHESIS CO., LTD.) manufactured by BASF PAN), 0.04 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name: IRGACURE369, manufactured by BASF JAPAN), and 0.04 parts by mass of ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (photoinitiator: product name IRGACURE OXE02 (manufactured by BASF JAPAN)) 0.02 parts by mass, fluorine-based surfactant (product name MEGAFACE R-08MH, manufactured by DIC) 0.07 parts by mass, and PGMEA7.14 parts by mass to obtain a photosensitive colored resin composition G-1 for a color filter.

(examples 2 to 26)

(1) Production of color Material Dispersion liquids G-2 to G-26

In example 1 (1), except that the block copolymer A-1 was replaced by one or more other block copolymers shown in tables 5 to 7, the solid content was the same as the block copolymer A-1 by mass, using synthesis example 2 ~ 3 of block copolymer A-2 ~ A-3, synthesis example 4 ~ 10 salt type block copolymer A-4 ~ A-10 solution, synthesis example 18 ~ 21 of block copolymer A-18 ~ A-21, synthesis example 26 ~ 32 of block copolymer A-26 ~ A-32, synthesis example 33 ~ 34 of block copolymer A-33 ~ A-34, synthesis example 35 ~ 37 salt type block copolymer A-35 ~ A-37 solution, and the total to 100 parts by mass of the regulation of PGMEA amount, color material dispersions G-2 to G-26 were obtained in the same manner as in (1) of example 1.

(2) Production of photosensitive colored resin compositions G-2 to G-26 for color Filter

Photosensitive colored resin compositions G-2 to G-26 for color filters were obtained in the same manner as in (2) of example 1, except that the color material dispersions G-2 to G-26 were used in place of the color material dispersion G-1 in (2) of example 1.

(example 35)

(1) Production of color Material Dispersion G-27

A color material dispersion G-27 was obtained by placing 23.25 parts by mass of the block copolymer A-23.25 parts by mass of Synthesis example 2 as a dispersant, 13 parts by mass of C.I. pigment Green 59(PG59, trade name FASTOGEN GREEN C100, available from DIC Co., Ltd.) as a color material, 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm in a mayonnaise bottle, shaking the resultant solution for 1 hour with a pigment shaker (available from Kubota corporation) as a pre-pulverization, then taking out the zirconia beads having a particle diameter of 2.0mm, adding 200 parts by mass of the zirconia beads having a particle diameter of 0.1mm, and similarly dispersing the resultant solution for 4 hours with a pigment shaker as a main pulverization.

(2) Production of photosensitive colored resin composition G-27 for color Filter

A photosensitive colored resin composition G-27 for a color filter was obtained in the same manner as in (2) of example 1, except that the color material dispersion liquid G-27 was used in place of the color material dispersion liquid G-1 in (2) of example 1.

(examples 36 to 38)

(1) Production of color Material Dispersion liquids G-28 to G-30

In example 35 (1), color material dispersions G-28 to G-30 were obtained in the same manner as in example 35 (1), except that the salt-type block copolymer a-8 solution of synthesis example 8, the block copolymer a-33 of synthesis example 33, and the salt-type block copolymer a-35 solution of synthesis example 35 were used so that the solid content was the same parts by mass as that of the block copolymer a-2, and the PGMEA amount was adjusted to 100 parts by mass in total, as shown in table 8, instead of the block copolymer a-2, respectively.

(2) Production of photosensitive colored resin compositions G-28 to G-30 for color Filter

Photosensitive colored resin compositions G-28 to G-30 for color filters were obtained in the same manner as in (2) of example 35, except that the above-mentioned color material dispersions G-28 to G-30 were used in place of the color material dispersion G-27 in (2) of example 35.

(example 39)

A color material dispersion G-31 was obtained in the same manner as in (1) of example 1 except that C.I. pigment Green 59(PG59, trade name FASTOGEN GREEN C100, manufactured by DIC) was used in place of C.I. pigment Green 58(PG58) as the color material in (1) of example 1 and that block copolymer A-2 of Synthesis example 2 was used in place of block copolymer A-1 of Synthesis example 1 as the dispersant.

(2) Production of photosensitive colored resin composition G-31 for color Filter

A photosensitive colored resin composition G-31 for a color filter was obtained in the same manner as in (2) of example 1, except that the color material dispersion liquid G-31 was used in place of the color material dispersion liquid G-1 in (2) of example 1.

(examples 40 to 42)

(1) Production of color Material Dispersion liquids G-32 to G-34

In example 39 (1), color material dispersions G-32 to G-34 were obtained in the same manner as in example 39 (1), except that the salt-type block copolymer a-8 solution of synthesis example 8, the salt-type block copolymer a-33 of synthesis example 33, and the salt-type block copolymer a-35 solution of synthesis example 35 were used in place of the block copolymer a-2, respectively, as shown in table 8, so that the solid content was the same parts by mass as the block copolymer a-2, and the PGMEA amount was adjusted to 100 parts by mass in total, as in example 39 (1).

(2) Production of photosensitive colored resin compositions G-32 to G-34 for color Filter

Photosensitive colored resin compositions G-32 to G-34 for color filters were obtained in the same manner as in (2) of example 39, except that the above-mentioned color material dispersions G-32 to G-34 were used in place of the color material dispersion G-31 in (2) of example 39.

Comparative examples 1 to 14

(1) Production of comparative color Material dispersions G-1 to G14

Comparative color material dispersions G-1 to G-14 were obtained in the same manner as in (1) of example 1 except that, in place of the block copolymer A-1, as shown in tables 5 to 7, the block copolymers A-11 to A-13 of Synthesis examples 11 to 13, the salt-type block copolymer A-14 to A-17 solutions of Synthesis examples 14 to 17, the block copolymers A-22 to A-25 of Synthesis examples 22 to 25 and the block copolymers A-38 to A-40 of Synthesis examples 38 to 40 were used in such a manner that the solid content was the same as that of the block copolymer A-1, and the PGMEA amount was adjusted to 100 parts by mass in total in (1) of example 1.

(2) Production of photosensitive colored resin compositions G-1 to G-14 for comparative color Filter

Photosensitive colored resin compositions G-1 to G-14 for comparative color filters were obtained in the same manner as in (2) of example 1, except that the comparative color material dispersions G-1 to G-11 were used in place of the color material dispersion G-1 in (2) of example 1.

(example 27)

(1) Production of color Material Dispersion R-1

13.25 parts by mass of the block copolymer A-13.25 parts by mass of Synthesis example 1, 6.5 parts by mass of C.I. pigment Red 177(PR177), 6.5 parts by mass of C.I. pigment Red 254(PR254), 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0mm were put in a mayonnaise bottle, and vibrated for 1 hour with a pigment vibrator (manufactured by Kubota Seiko Co., Ltd.) to prepare pre-ground, followed by taking out the zirconia beads having a particle diameter of 2.0mm, adding 200 parts by mass of the zirconia beads having a particle diameter of 0.1mm, and similarly dispersed for 4 hours with a pigment vibrator to prepare a color material dispersion liquid R-1.

(2) Production of photosensitive colored resin composition R-1 for color Filter

To the color material dispersion liquid R-111.40 parts by mass obtained in the above-mentioned (1), 0.64 part by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 0.60 part by mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by TOYOBO SYNTHESIS CO., LTD.), 0.09 part by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name: IRGACURE907, manufactured by BASF JAPAN), 0.04 part by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name: IRGACURE369, manufactured by BASF JAPAN), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (photoinitiator: product name IRGACURE OXE02 (manufactured by BASF JAPAN)) 0.02 parts by mass, fluorine-based surfactant (product name MEGAFACE R-08MH, manufactured by DIC) 0.07 parts by mass, and PGMEA7.14 parts by mass to obtain a photosensitive colored resin composition R-1 for a color filter.

(examples 28 to 30)

(1) Production of color Material Dispersion liquids R-2 to R-4

Color material dispersions R-2 to R-4 were obtained in the same manner as in (1) of example 27 except that the block copolymers a-27 and a-3 and the salt-type block copolymer a-4 solutions of synthesis examples 27, 3 and 4 were used so that the solid content was the same mass as that of the block copolymer a-1, respectively, and the amount of PGMEA was adjusted to 100 mass parts in total, as shown in table 9, instead of the block copolymer a-1 in (1) of example 27.

(2) Production of photosensitive colored resin compositions R-2 to R-4 for color Filter

Photosensitive colored resin compositions R-2 to R-4 for color filters were obtained in the same manner as in (2) of example 27 except that the color material dispersions R-2 to R-4 were used in place of the color material dispersion R-1 in (2) of example 27.

Comparative examples 15 to 18

(1) Production of comparative color Material dispersions R-1 to R-4

Comparative color material dispersions R-1 to R-4 were obtained in the same manner as in (1) of example 27, except that in (1) of example 27, the block copolymers a-11, a-13, a-24 and a-25 of synthesis examples 11, 13, 24 and 25 were used so that the solid content was the same mass parts as that of the block copolymer a-1, respectively, as shown in table 9, and the amount of PGMEA was adjusted to 100 mass parts in total, instead of the block copolymer a-1.

(2) Production of photosensitive colored resin compositions R-1 to R-4 for comparative color Filter

Photosensitive colored resin compositions R-1 to R-4 for comparative color filters were obtained in the same manner as in (2) of example 27 except that the comparative color material dispersions R-1 to R-4 were used in place of the color material dispersion R-1 in (2) of example 27.

(example 31)

(1) Production of color Material Dispersion B-1

13.25 parts by mass of the block copolymer A-13.25 parts by mass of Synthesis example 1, 10.4 parts by mass of C.I. pigment blue 15:6(PB15:6), 2.6 parts by mass of C.I. pigment Violet 23(PV23), 16.25 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0mm were put in a mayonnaise bottle, and vibrated for 1 hour with a pigment vibrator (manufactured by Kubotai iron Ltd.) to preliminarily pulverize, followed by taking out the zirconia beads having a particle size of 2.0mm, adding 200 parts by mass of the zirconia beads having a particle size of 0.1mm, and dispersed for 4 hours with a pigment vibrator similarly to preliminarily pulverize to obtain a color material dispersion B-1.

(2) Production of photosensitive colored resin composition B-1 for color Filter

To the dispersion liquid B-18.59 parts by mass of the coloring material obtained in the above-mentioned (1), 1.05 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 41, 0.98 parts by mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by TOYOBO SYNTHESIS CO., LTD.), 0.15 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name: IRGACURE907, (manufactured by TOYOBO CO., LTD.) manufactured by BASF PAN), 0.07 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name: IRGACURE369, manufactured by BASF PAN), and 0.07 parts by mass of ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (photoinitiator: product name IRGACURE OXE02 (manufactured by BASF JAPAN)) 0.03 parts by mass, a fluorine-based surfactant (product name MEGAFACE R-08MH, manufactured by DIC) 0.07 parts by mass, and PGMEA9.06 parts by mass to obtain a photosensitive colored resin composition B-1 for a color filter.

(examples 32 to 34)

(1) Production of color Material Dispersion liquids B-2 to B-4

Color material dispersions B-2 to B-4 were obtained in the same manner as in (1) of example 31, except that the block copolymers a-27 and a-3 and the salt-type block copolymer a-4 solutions of synthesis examples 27, 3 and 4 were used so that the solid content was the same mass part as that of the block copolymer a-1, and the amount of PGMEA was adjusted to 100 mass parts in total, as shown in table 10, respectively, in (1) of example 31, instead of the block copolymer a-1.

(2) Production of photosensitive colored resin compositions B-2 to B-4 for color Filter

Photosensitive colored resin compositions B-2 to B-4 for color filters were obtained in the same manner as in (2) of example 31, except that the above-mentioned color material dispersions B-2 to B-4 were used in place of the color material dispersion B-1 in (2) of example 31.

Comparative examples 19 to 22

(1) Production of comparative color Material dispersions B-1 to B-4

Comparative color material dispersions B-1 to B-4 were obtained in the same manner as in (1) of example 31, except that in (1) of example 31, the block copolymers a-11, a-13, a-24 and a-25 of synthesis examples 11, 13, 24 and 25 were used, respectively, as shown in table 10, in place of the block copolymer a-1, so that the solid content was the same mass as that of the block copolymer a-1, and the PGMEA amount was adjusted to 100 mass parts in total.

(2) Production of photosensitive colored resin compositions B-1 to B-4 for comparative color Filter

Photosensitive colored resin compositions B-1 to B-4 for comparative color filters were obtained in the same manner as in (2) of example 31 except that the comparative color material dispersions B-1 to B-4 were used in place of the color material dispersion B-1 in (2) of example 31.

[ evaluation method ]

< evaluation of dispersibility of color Material Dispersion >

The viscosities of the color material dispersions obtained in examples and comparative examples were measured immediately after preparation and after storage at 25 ℃ for 30 days, and the viscosity change rate was calculated from the viscosities before and after storage to evaluate the viscosity stability. The viscosity at 25.0. + -. 0.5 ℃ was measured using a vibration viscometer for viscosity measurement. The results are shown in tables 5 to 10.

(evaluation criteria for Dispersion stability)

A: the viscosity change rate before and after storage is less than 15 percent

B: the viscosity change rate before and after storage is more than 15% and less than 25%

C: the viscosity change rate before and after storage is more than 25% and less than 40%

D: the viscosity change rate before and after storage is more than 40%

Here, it is a value when the color material is 13 mass% with respect to the total mass of the solvents containing the color material dispersion liquid.

The color material dispersion can be used in practice even if the evaluation result is C, but the color material dispersion is more favorable if the evaluation result is B, and the dispersion stability of the color material dispersion is excellent if the evaluation result is a.

< evaluation of optical Properties and evaluation of contrast >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were each coated on a Glass substrate (NH Techno Glass corporation, "NA 35") having a thickness of 0.7mm and 100mm × 100mm by using a spin coater, and then dried at 80 ℃ for 3 minutes by using a hot plate, thereby forming colored layers. Irradiating the colored layer with ultra-high pressure mercury lamp at 60mJ/cm²Ultraviolet rays of (1).

Then, the colored substrate was post-baked in a dust-free oven at 230 ℃ for 30 minutes, and the contrast, chromaticity (x, Y) and brightness (Y) of the resulting colored substrate were measured using a Saguchi contrast measuring instrument CT-1B manufactured by Katsuchi Electricity and a micro-spectrometer OSP-SP200 manufactured by Olympus. The results are shown in tables 5 to 10.

(reference for contrast evaluation)

A: green over 7000, Red over 5000 and Blue over 5000

B: 6300-7000 Green, 4300-5000 Red and 4300-5000 Blue

C: green is lower than 6300, Red is lower than 4300, Blue is lower than 4300

In the examples 1 to 26 and comparative examples 1 to 11, y is 0.570, y is 0.420, y is 0.480, Red is 0.650, and Blue is 0.107 in examples 27 to 30 and comparative examples 12 to 15, and Blue is 0.650, in examples 31 to 34 and comparative examples 16 to 19, respectively, under the C light source.

< evaluation of development residue >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied onto Glass substrates (NH Techno Glass corporation, "NA 35") having a thickness of 0.7mm and 100mm × 100mm, respectively, by using a spin coater, and then dried at 80 ℃ for 3 minutes by using a hot plate, thereby forming colored layers having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution. After the unexposed portion (50 mm. times.50 mm) of the glass substrate on which the colored layer was formed was visually observed, the glass substrate was sufficiently wiped with a lens cleaning cloth (manufactured by Toray corporation, trade name: TORAYSEE MK cleaning cloth) containing ethanol, and the degree of coloring of the lens cleaning cloth was visually observed. The results are shown in tables 5 to 10.

(evaluation criteria of development residue)

A: the development residue was not visually confirmed, and the lens cleaning cloth was completely free from coloring

B: slight coloring of the lens cleaning cloth was confirmed by visual observation without confirming the development residue

C: slight development residue was visually observed and slight coloring of the lens cleaning cloth was observed

D: slight development residue was visually observed and coloring of the lens cleaning cloth was observed

E: the development residue was visually confirmed and the coloring of the lens cleaning cloth was confirmed

When the evaluation criterion of the development residue is A, B or C, the development residue is evaluated to be sufficiently suppressed, and the evaluation can be used practically without any problem.

< evaluation of development adhesion >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied onto Glass substrates (NH Techno Glass corporation, "NA 35") having a thickness of 0.7mm and 100mm × 100mm, respectively, by using a spin coater, and then dried at 80 ℃ for 3 minutes by using a hot plate, thereby forming colored layers having a thickness of 2.5 μm. Irradiating the colored layer with an ultra-high pressure mercury lamp through a photomask having a shielding opening width of 2-80 μm to obtain a 60mJ/cm²Ultraviolet rays of (1). The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution. The developed substrate was observed with an optical microscope to observe the presence or absence of a colored layer having a line width corresponding to the mask opening. The results are shown in tables 5 to 10.

(evaluation criteria for development adhesion)

A: the colored layer was observed in the portion where the line width of the shadow opening was less than 10 μm

B: the colored layer is observed in the portion of the shielding opening with a line width of 10 μm or more and less than 20 μm

C: the colored layer is observed in the part with the line width of more than 20 μm and less than 50 μm of the shielding opening

D: the colored layer is observed in the part with the line width of the shielding opening more than 50 μm and less than 80 μm

E: no coloring layer was observed in the portion where the line width of the shielding opening was 80 μm or less

Even if the evaluation result is C, the color filter used in the photosensitive colored resin composition can be used in practice; however, if the evaluation result is B, the photosensitive colored resin composition for a color filter is suitable for the case of higher refinement; if the evaluation result is A, the photosensitive colored resin composition for a color filter can be suitably used in the case of further higher refinement.

< evaluation of solvent redissolution >

The front end of a glass substrate having a width of 0.5cm and a length of 10cm was immersed in the photosensitive colored resin composition for a color filter obtained in examples and comparative examples, and applied to a portion having a length of 1cm of the glass substrate. The pulled glass substrate was placed in a constant temperature and humidity machine so that the glass surface was horizontal, and dried at a temperature of 23 ℃ and a humidity of 80% RH for 30 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. The redissolved state of the dried coating film at this time was visually judged and evaluated. The results are shown in tables 5 to 10.

(evaluation criteria for solvent redissolution)

A: the dried coating film is completely dissolved

B: flakes which produce a dry coating in a solvent, the flakes being dissolved shortly after

C: flakes giving a dry coating in a solvent, solution colouring

D: flakes producing a dry coating in solvent, the solution being uncolored

E: flakes having no dried coating film in solvent, solution of the flakes being uncolored

When the evaluation standard of the development residue is A, B or C, the solvent re-solubility is good and the residue can be used practically without any problem.

[ Table 5]

[ Table 6]

[ Table 7]

Table 7.

[ Table 8]

Table 8.

[ Table 9]

Table 9.

[ Table 10]

Table 10.

[ integration of results ]

As is apparent from the results in tables 1 to 10, a block copolymer containing an a block containing a constituent unit represented by the above general formula (I) and a B block containing a constituent unit derived from a carboxyl group-containing monomer and having solventropic properties was used as a dispersant; and at least a part of the nitrogen site of the constituent unit represented by the general formula (I) of the block copolymer, and at least one dispersant of salt type block copolymers formed by salt with at least 1 or more compounds selected from the group consisting of compounds represented by the following general formulas (1) to (3), wherein the acid value of the dispersant is 1 to 18mgKOH/g, and the glass transition temperature of the dispersant is 30 ℃ or higher. The photosensitive colored resin compositions for color filters of examples 1 to 42 prepared using the color material dispersions of examples 1 to 42 were excellent in color material dispersion stability, development adhesion and solvent resolubility while suppressing the occurrence of development residues.

Among them, examples 4 to 10 and 24 to 26, 30, 34, 36, 38, 40 and 42 using the salt block copolymer are particularly excellent in color material dispersibility, and the obtained colored layer is excellent in contrast.

On the other hand, although the glass transition temperature of the dispersant was 30 ℃ or higher, the development adhesion of comparative examples 1, 2, 12 to 14, 15 and 19 having an acid value higher than the specific value in the present application was poor, and the solvent resolubility of comparative examples 2 and 12 to 14 having a higher acid value was also poor. On the other hand, the glass transition temperature of the dispersant was 30 ℃ or higher, but the evaluation of the development residue was poor in comparative examples 3 to 7, 16 and 20, which had an acid value lower than the specific value of the present application. Although the acid value of the dispersant was the specified value, the development adhesion was poor in comparative examples 8 to 10, 17 and 21 in which the glass transition temperature of the dispersant was lower than the specified value. In addition, the dispersant of 23 ℃ glass transition temperature, acid value higher than the present value of comparative examples 11, 18 and 22 development adhesion is poor.

Example II series: first embodiment of the second aspect of the present invention

Synthesis example II-1 preparation of dispersant a

A500 ml four-necked separable flask was dried under reduced pressure, and then replaced with Ar (argon).

While Ar purging was performed, dehydrated THF100g, methyltrimethylsilyldimethylketene acetal 2.0g, a 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoic acid (TBACB) 0.15ml, and mesitylene 0.2g were added. Therein, using a dropping funnel, 36.7g of Methyl Methacrylate (MMA) was added dropwise over 45 minutes. Since the reaction proceeded with heat generation, the temperature was kept below 40 ℃ by ice bath cooling. After 1 hour, 13.3g of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After 1 hour of the reaction, 5g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to give block copolymer II-A1. The mass average molecular weight was 6,000 and the amine value was 95mgKOH/g as determined by GPC measurement (NMP LiBr10 mM).

In a 100mL round-bottomed flask, 29.35 parts by mass of block copolymer a-1 was dissolved in 29.35 parts by mass of PGMEA, 3.17 parts by mass (0.20 mol per 1 mol of DMMA units of block copolymer 1 in the compound represented by the above general formula (3)) of phenylphosphonic acid (PPA, manufactured by tokyo chemical synthesis) as the compound represented by the above general formula (3) was added, and the mixture was stirred at a reaction temperature of 30 ℃ for 20 hours to obtain a salt-type block copolymer II-a1 (dispersant a) solution. The amine value after the salt formation is specifically calculated as follows.

An NMR sample tube was charged with 1g of a solution prepared by mixing 9 parts by mass of the salt type block copolymer II-A1 (solid matter after reprecipitation) and 91 parts by mass of chloroform-D1 NMR, and the 13C-NMR spectrum was measured at room temperature and the number of accumulations 10000 times using a nuclear magnetic resonance apparatus (FT NMR, JNM-AL 400). In the obtained spectral data, the ratio of the number of amino groups to the total number of amino groups to be salified was calculated from the ratio of the integrated values of the peak of carbon atoms adjacent to nitrogen atoms not salified and the peak of carbon atoms adjacent to nitrogen atoms to be salified at the terminal nitrogen site (amino group), and it was confirmed that there was no difference from the theoretical salt formation ratio (all of 2 acidic groups of phenylphosphonic acid formed salts with the terminal nitrogen site of DMMA of block copolymer II-a 1).

The amine value after salt formation was calculated to be 57mgKOH/g by subtracting the amine value (38mgKOH/g) of 0.40 molar parts of DMMA units from the amine value before salt formation of 95 mgKOH/g. The Tg's of the block copolymers before and after salt formation are shown in Table 11.

(Synthesis example II-2: preparation of dispersant b)

The procedure was carried out in the same manner as in Synthesis example 8, series I, salt-type block copolymer A-8 to obtain a solution of salt-type block copolymer II-A2 (dispersant b). The acid value of the block copolymer after salt formation was the same as that of the block copolymer II-A2 before salt formation, and the amine value after salt formation was calculated specifically in the same manner as in Synthesis example II-1.

(Synthesis example II-3: preparation of dispersant c)

While Ar purging was performed, 100g of dehydrated THF, 2.0g of methyltrimethylsilyldimethylketene acetal, 0.15ml of a 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoic acid (TBACB), and 0.2g of mesitylene were added. Using a dropping funnel, 33g of methyl methacrylate was added dropwise over 45 minutes. Since the reaction proceeded with heat generation, the temperature was kept below 40 ℃ by ice bath cooling. After 1 hour, 17g of dimethylaminoethyl methacrylate was added dropwise over 15 minutes. After 1 hour of the reaction, 5g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to give block copolymer II-A3. The mass-average molecular weight determined by GPC measurement (NMPLiBr10mM) was 6,000, and the amine value was 120 mgKOH/g.

In a 100mL round-bottomed flask, 24.15 parts by mass of block copolymer II-A3 was dissolved in 24.15 parts by mass of PGMEA, 3.5 parts by mass of phenylphosphonic acid (manufactured by Tokyo chemical conversion) as the compound represented by the above general formula (3) (0.20 mol based on 1 mol of DMMA unit of block copolymer II-A3 as the compound represented by the above general formula (3)) was added, and the mixture was stirred at a reaction temperature of 30 ℃ for 20 hours to obtain a salt-type block copolymer II-A3 (dispersant c) solution having a solid content of 20% by mass. Specifically, the amine value after the salt formation was calculated in the same manner as in Synthesis example II-1.

(Synthesis example IJ-4: Synthesis of dispersant d)

Synthesis of a solution of the block copolymer II-A4 before salt formation and a salt-type block copolymer (dispersant d) was carried out in the same manner as in Synthesis example II-2 except that the contents in Synthesis example 1I-2 were changed to those shown in Table 11. In Synthesis example II-4, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. The acid values, Tg and amine values of the obtained block copolymer before salt formation and the salt block copolymer are shown in Table 11.

(Synthesis example II-5: Synthesis of dispersant e)

A block copolymer II-A5 (dispersant e) was synthesized in the same manner as in the preparation of the pre-salified block copolymer II-A2 (acid value: 8mgKOH/g, Tg38 ℃ C.) of Synthesis example II-2.

(Synthesis examples II-6 to II-7: Synthesis of dispersant f and dispersant g)

Synthesis examples II-5 were repeated in the same manner as in Synthesis example II-5 except that the monomers and contents shown in Table 11 were changed to synthesize a block copolymer II-A6 (dispersant f) and a block copolymer II-A7 (dispersant g). The acid value, Tg and amine value of the obtained block copolymer are shown in Table 11.

(Synthesis example II-8: preparation of dispersant h)

Synthesis of Synthesis example II-2A block copolymer II-A8 before salt formation was synthesized in the same manner as in Synthesis example II-2 except that the monomers and the contents were changed as shown in Table 11. Using this pre-salifying block copolymer II-A8, a salt-forming block copolymer II-A8 (dispersant h) solution was obtained in the same manner as in Synthesis example II-2, except that the amount of the salt-forming compound was changed to the amount shown in Table 11. The acid values, Tg and amine values of the obtained block copolymer before salt formation and the salt block copolymer are shown in Table 11.

(Synthesis example II-9: Synthesis of alkali-soluble resin A solution)

A mixture of 40 parts by mass of BzMA, 15 parts by mass of MMA, 25 parts by mass of MAA and 3 parts by mass of AIBN was added dropwise to a polymerization vessel containing 150 parts by mass of PGMEA at 100 ℃ for 3 hours under a nitrogen stream. After the completion of the dropwise addition, the mixture was further heated at 100 ℃ for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7000.

Subsequently, 20 parts by mass of GMA, 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110 ℃ for 10 hours to cause a reaction between the carboxylic acid group of the main chain methacrylic acid and the epoxy group of glycidyl methacrylate. In the reaction, air was bubbled into the reaction solution in order to prevent polymerization of glycidyl methacrylate. The reaction was followed by measuring the acid value of the solution. The obtained alkali-soluble resin a was obtained by introducing a side chain having an ethylenic double bond to the main chain formed by copolymerization of BzMA, MMA and MAA using GMA, and had an acid value of 74mgKOH/g and a weight-average molecular weight of 12000 in a solid content of 40 mass%.

[ Table 11]

The abbreviations in the tables are as follows.

PME-200: methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by Nichikoku K.K., BLEMMER-PME-200, ethyleneoxy repeat number ═ 4)

DMAPMA: dimethylaminopropyl methacrylamide

(example II-1)

(1) Production of color Material Dispersion liquid II-G1

6.18 parts by mass of the dispersant b solution of Synthesis example II-2 as a dispersant, 13.00 parts by mass of C.I. pigment Green 59(PG59, trade name: FASTOGEN GREEN C100, available from DIC Co., Ltd.) as a color material, 14.63 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 9, 66.19 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0mm were placed in a mayonnaise bottle, and vibrated for 1 hour with a pigment vibrator (available from light Seikagaku corporation) to preliminarily pulverize the beads, then the zirconia beads having a particle size of 2.0mm were taken out, 200 parts by mass of the zirconia beads having a particle size of 0.1mm were added, and dispersed for 4 hours in the same manner as the pigment vibrator to obtain a color material dispersion liquid II-G1.

(2) Production of photosensitive colored resin composition II-G1 for color Filter

To the color material dispersion liquid II-G111.40 parts by mass obtained in the above (1), 0.64 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example II-9, 0.60 parts by mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by TOYOBO SYNTHESIS CO., LTD.), 0.09 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name: IRGACURE907, manufactured by BASF Co., Ltd.), 0.04 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name: IRGACURE369, manufactured by BASF Co., Ltd.), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, a fluorine-based surfactant (trade name MEGAFACE F559, manufactured by DIC corporation) 0.07 parts by mass, and PGMEA7.14 parts by mass to obtain photosensitive colored resin compositions II-G1 for color filters.

(3) Formation of colored layer

The photosensitive colored resin compositions II to G1 obtained in the above (2) were applied to Glass substrates (NH Techno Glass, "NA 35", Inc.) having a thickness of 0.7mm and 100mm X100 mm by using a spin coater, respectively, and then dried at 80 ℃ for 3 minutes by using a hot plate, and irradiated with 60mJ/cm by using an ultra-high pressure mercury lamp²The resultant was post-baked in a dust-free oven at 230 ℃ for 30 minutes to adjust the film thickness so that the chromaticity under the C light source was 0.4 for y and 0.2 for x, thereby forming a colored layer II-G1.

(examples II-2 to II-10 and comparative examples II-C1 to II-C4)

(1) Production of colorant Dispersion liquids II-G2-II-G6 and II-CG 1-II-CG 4

In example II-1 (1), color material dispersions II-G2 to II-G6 and II-CG1 to II-CG4 were obtained in the same manner as in example II-1 (1) except that the type and the amount of the dispersant used were changed so that the solid content was the same part by mass, the color material was partially changed in the comparative example, and the amount of PGMEA was adjusted to 100 parts by mass in total, instead of the dispersant b solution, as shown in Table 12.

(2) Production of photosensitive colored resin compositions II-G2-II-G6 and II-CG 1-II-CG 4 for color Filter

Photosensitive colored resin compositions II-G2 to II-G6 and II-CG1 to II-CG4 for color filters were obtained in the same manner as in (2) of example II-1 except that the above-mentioned color material dispersions II-G2 to II-G6 and II-CG1 to II-CG4 were used in place of the color material dispersion II-G1 in (2) of example II-1 in examples II-2 to II-6 and comparative examples II-C1 to II-C4, respectively.

(3) Formation of colored layer

In example II-1 (3), colored layers II-G2 to II-G6 and II-CG1 to II-CG4 were obtained in the same manner as in example II-1 (3) except that the photosensitive colored resin compositions II-G2 to II-G6 and II-CG1 to II-CG4 were used in place of the photosensitive colored resin composition II-G1, respectively.

(examples II-7 to II-10)

(1) Production of photosensitive colored resin compositions II-G7-II-G10 for color Filter

Photosensitive colored resin compositions II-G7 to II-G10 for color filters were obtained in the same manner as in (2) of example II-1 except that the photoinitiators were changed to those shown in Table 12 in examples II-7 to II-10.

In example II-9, the procedure was carried out in the same manner as in (2) in example II-1 except that 0.10 part by mass of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) and 0.05 part by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name IRGACURE907, (manufactured by BASF; IRG907), and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF, IRG369) were used instead of 0.02 part by mass of 1- (o-acetyloxime) in (2) in example II-1, a photosensitive colored resin composition II-G9 for a color filter was obtained.

(3) Formation of colored layer

Colored layers II-G7 to II-G10 were obtained in the same manner as in (3) of example II-1, except that the photosensitive color resin compositions II-G7 to II-G10 were used in place of the photosensitive color resin composition II-G1 in (3) of example II-1.

Comparative example II-C5

In comparative example II-C5, a colored layer II-CG5 was formed in the same manner as in (3) of example II-1, except that the photosensitive colored resin composition II-CG2 obtained in comparative example IJ-C2 was used in place of the photosensitive colored resin composition II-G1 in (3) of example II-1, and the colored layer was formed by adjusting the film thickness so that the chromaticity at the C light source was 0.50.

[ Table 12]

The table is abbreviated as follows.

G58: pigment Green 58 (trade name: FASTOGEN GREEN A110, available from DIC corporation)

G7: pigment Green 7 (trade name: CHROMOFINE GREEN 6428EC, manufactured by Dai chemical industry Co., Ltd.)

byk-161: disperbyk-161(BYK Chemie, urethane dispersant, solid content 30% by mass)

PB 822: ajisper PB822 (monosodium glutamate FINE TECHNO, polyester dispersant, solid content 30 wt%)

NCI-831: oxime ester photoinitiators (ADEKA ARKLS NCI-831, manufactured by ADEKA)

TR-PBG-304: oxime ester photoinitiators (manufactured by Changzhou powerful New electronic Material Co., Ltd.)

OXE 03: oxime ester photoinitiators (IRGACURE OXE-03, BASF.)

NCI-930: oxime ester photoinitiators (ADEKA ARKLS NCI-930, manufactured by ADEKA)

[ evaluation method ]

< evaluation of dispersibility of color Material Dispersion >

The viscosities of the color material dispersions obtained in examples and comparative examples were measured immediately after preparation and after storage at 25 ℃ for 30 days, and the viscosity change rate was calculated from the viscosities before and after storage to evaluate the viscosity stability. The viscosity at 25.0. + -. 0.5 ℃ was measured using a vibration viscometer for viscosity measurement. The results are shown in Table 12.

(evaluation criteria for Dispersion stability)

A: the viscosity change rate before and after storage is less than 10%

B: the viscosity change rate before and after storage is more than 10% and less than 15%

C: the viscosity change rate before and after storage is more than 15% and less than 25%

D: the viscosity change rate before and after storage is more than 25%

< evaluation of optical Properties and evaluation of contrast >

The contrast, chromaticity (x, Y) and brightness (Y) of the colored layers obtained in examples and comparative examples were measured by using a saxaban electrical contrast measuring apparatus CT-1B and an Olympus micro-spectrometer OSP-SP 200.

In comparative example 1 in which PG58 was used as a pigment, the chromaticity of y 0.4 and the chromaticity of x 0.2 under the C light source could not be achieved.

The results are shown in Table 12.

(color gamut evaluation criteria)

A value when y is 0.4 to 0.5 under the C light source

A: x is less than 0.21

B：x＝0.21～0.23

C: x is more than 0.23

(evaluation criterion of luminance)

C light source is set to a value when y is 0.4 and x is 0.2

A: over 50.0

B：47.5～50.0

C: less than 47.5

C light source, when y is 0.5

A: over 30.0

B：30.0～25.0

C: less than 25.0

(reference for contrast evaluation)

C light source is set to a value when y is 0.4 and x is 0.2

A: over 15000

B：13500～15000

C: less than 13500

C light source, when y is 0.5

A: over 3500

B：2500～3500

C: less than 2500

< evaluation of solvent redissolution >

The front end of a glass substrate having a width of 0.5cm and a length of 10cm was immersed in the photosensitive colored resin composition for a color filter obtained in examples and comparative examples, and applied to a portion having a length of 1cm of the glass substrate. The pulled glass substrate was placed in a constant temperature and humidity machine so that the glass surface was horizontal, and dried at a temperature of 23 ℃ and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film was attached was immersed in PGMEA for 15 seconds. The redissolved state of the dried coating film at this time was visually judged and evaluated. The results are shown in Table 12.

(evaluation criteria for solvent redissolution)

A: the dried coating film is completely dissolved

B: flakes giving a dry coating in a solvent, solution colouring

C: flakes having no dried coating film in solvent, solution of the flakes being uncolored

The above evaluation criterion is practically usable when a or B is used, and the effect is more excellent when a is used as the evaluation result.

< evaluation of development residue >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied onto Glass substrates (NH Techno Glass corporation, "NA 35") having a thickness of 0.7mm and 100mm × 100mm, respectively, by using a spin coater, and then dried at 60 ℃ for 3 minutes by using a hot plate, thereby forming colored layers having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution. After the unexposed portion (50 mm. times.50 mm) of the glass substrate on which the colored layer was formed was visually observed, the glass substrate was sufficiently wiped with a lens cleaning cloth (manufactured by Toray corporation, trade name: TORAYSEE MK cleaning cloth) containing ethanol, and the degree of coloring of the lens cleaning cloth was visually observed. The results are shown in Table 12.

(evaluation criteria of development residue)

A: no development residue was visually recognized, and the lens cleaning cloth was completely free from coloring.

B: the development residue was not visually recognized, and slight coloring of the lens cleaning cloth was recognized.

C: slight development residue was visually observed, and slight coloring of the lens cleaning cloth was observed.

D: a slight development residue was visually observed, and coloring of the lens cleaning cloth was observed.

E: the development residue was visually observed and the coloring of the lens cleaning cloth was observed.

The evaluation criteria A, B or C are practically applicable, and the effect is more excellent when the evaluation result is B, and further a.

< evaluation of development adhesion >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied onto Glass substrates (NH Techno Glass corporation, "NA 35") having a thickness of 0.7mm and 100mm × 100mm, respectively, by using a spin coater, and then dried at 60 ℃ for 3 minutes by using a hot plate, thereby forming colored layers having a thickness of 2.5 μm. Irradiating the colored layer with an ultra-high pressure mercury lamp through a photomask having a shielding opening width of 2-80 μm to obtain a 60mJ/cm²Ultraviolet rays of (1). The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution. The developed substrate was observed with an optical microscope to observe the presence or absence of a colored layer having a line width corresponding to the mask opening. The results are shown together in Table 12.

(evaluation criteria for development adhesion)

A: the colored layer was observed in a portion where the line width of the shadow opening was less than 10 μm.

B: the colored layer is observed in a portion where the width of the shielding opening is 10 μm or more and less than 20 μm.

C: the colored layer is observed in a portion where the width of the shielding opening is 20 μm or more and less than 50 μm.

D: the colored layer is observed in a portion where the width of the shielding opening is 50 μm or more and less than 80 μm.

E: no coloring layer was observed in a portion where the line width of the shielding opening was 80 μm or less.

When the evaluation criterion is A, B or C, the method is practical; however, if the evaluation result is B or A, the photosensitive colored resin composition for a color filter is suitable for use in higher fineness.

< evaluation of development resistance >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were each coated on a Glass substrate (manufactured by NH Techno Glass corporation, "NA 35") having a thickness of 0.7mm by using a spin coater. Drying at 80 deg.C for 3 min, and irradiating with ultra-high pressure mercury lamp to obtain a dry powder of 40mJ/cm²Ultraviolet rays of (1). The film thickness at this time was measured and designated as T1 (. mu.m). Thereafter, shower development was performed using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution. The film thickness after development was measured as T2 (. mu.m). T2/T1X 100 (%) was calculated. The results are shown in Table 12.

(evaluation criteria for development resistance)

A: more than 95 percent

B: more than 90 percent and less than 95 percent

C: less than 90 percent

The evaluation result is B, which is practically usable, but the effect is more excellent if the evaluation criterion is a.

< evaluation of Water bleed >

The photosensitive colored resin compositions for color filters obtained in examples and comparative examples were applied onto a GLASS substrate ("NA 35", manufactured by NH techon GLASS corporation) by a spin coater in such a thickness that a colored layer having a thickness of 1.6 μm was formed after post-baking, dried at 60 ℃ for 3 minutes by using a hot plate, and irradiated over the entire surface by an ultra-high pressure mercury lamp without passing through a photomask at 60mJ/cm²The ultraviolet ray of (2) forms a colored layer on the glass substrate. Next, the substrate was subjected to spin development using 0.05 wt% potassium hydroxide (KOH) as a developer, and after 60 seconds of contact with the developer, the substrate was washed with pure water to perform a development treatment, and after the washed substrate was spun for 10 seconds to remove water by centrifugation, immediately after which the contact angle of pure water was measured as described below to evaluate water bleeding.

The contact angle of pure water was measured as: to the surface of the colored layer immediately after the water was removed by centrifugation, a droplet of 1.0. mu.L of pure water was dropped, and the static contact angle after 10 seconds of dropping was measured by the θ/2 method. The measurement apparatus used a contact angle meter DM500 manufactured by kyowa interface science.

(evaluation criteria)

A: the contact angle is more than 80 DEG

B: the contact angle is more than 65 degrees and less than 80 degrees

C: the contact angle is more than 50 degrees and less than 65 degrees

D: contact angle less than 50 DEG

If the water bleeding evaluation standard is A or B, the method can be used in practice; however, when the evaluation result is a, the effect is more excellent.

[ integration of results ]

As is apparent from the results in table 12, the color material dispersions of examples II-1 to II-6, in which c.i. pigment green 59 was combined with a dispersant which is a polymer having a constituent unit represented by general formula (I), had good viscosity stability. On the other hand, the viscosity stability of the color material dispersions of comparative examples II-C3 to II-C4, in which a urethane dispersant and a polyester dispersant were combined with C.I. pigment Green 59, was significantly deteriorated. In addition, the viscosity stability of the color material dispersion liquid of comparative example II to C2, in which c.i. pigment green 7 was combined with a dispersant which is a polymer having a constituent unit represented by general formula (I), was remarkably deteriorated.

The photosensitive colored resin compositions for color filters of examples II-1 to II-10, in which c.i. pigment green 59 was combined with a dispersant which is a polymer having a constitutional unit represented by general formula (I), were remarkably high in luminance, while showing a region where x was 0.20 when y was 0.40 or showing a bluish green color in a region where x was 0.16 when y was 0.50. The photosensitive colored resin compositions for color filters of examples II-1 to II-10, in which C.I. pigment Green 59 was combined with a dispersant which was a polymer having a constitutional unit represented by the general formula (I), were excellent in dispersion stability of the coloring material, excellent in contrast, excellent in solvent re-solubility, and further suppressed in the generation of development residue.

Wherein a block copolymer comprising an A block comprising a constituent unit represented by the above general formula (I) and a B block comprising a constituent unit derived from a carboxyl group-containing monomer and having solventropic properties is used as a dispersant; or a salt-type block copolymer which forms a salt with at least a part of the nitrogen site of the constituent unit represented by the general formula (I), wherein the acid value of the dispersant is 1mgKOH/g or more and 18mgKOH/g or less, and the glass transition temperature of the dispersant is 30 ℃ or more, particularly development residue generation is suppressed, and development adhesion is excellent in examples II-1, 2, 3, 6 to 10.

On the other hand, when c.i. pigment green 58 was used as in comparative example II-C1, when y was 0.4, the region where x was 0.2 could not be displayed. When c.i. pigment green 7 was used as in comparative example II to C2, the luminance was low in the region where y was 0.4, although x was 0.2. When c.i. pigment green 7 was used as in comparative example II-C5, when y was 0.50, a region where x was 0.16 was displayed, but the brightness was low. Although not shown in the table, the c.i. pigment green 58 cannot show a region where x is 0.16 when y is 0.50.

In addition, when c.i. pigment green 7 was used as in comparative examples II to C2, the dispersibility was poor even when a dispersant was used in combination as a polymer having a constituent unit represented by the general formula (I), and the contrast was low, and the re-solubility and the residue were also deteriorated.

On the other hand, the photosensitive colored resin compositions for color filters of comparative examples II-C3 to II-C4, in which a urethane based dispersant or a polyester based dispersant was combined with c.i. pigment green 59, had inferior dispersibility, and therefore, the luminance was lower than in the examples, the contrast was low, and the re-solubility and the residue were also inferior.

In the examples, the effect of suppressing the development resistance and the occurrence of water bleeding was significantly increased in the examples using the oxime ester photoinitiator as the photoinitiator.

Example series III: second aspect of the present invention

Solutions of dispersants a to h in the series of example III were obtained in the same manner as in Synthesis examples II-1 to II-8 of the series of example II, respectively. The alkali-soluble resin A solution was obtained in the same manner as in Synthesis example II-9 of example II series.

(example III-1)

(1) Production of color Material Dispersion III-G1

6.22 parts by mass of a dispersant b solution as a dispersant, 5.33 parts by mass of a C.I. pigment Green 59(PG59, trade name FASTOGEN GREEN C100, available from DIC corporation) as a color material, and 7.67 parts by mass of a C.I. pigment YELLOW 138(PY138, trade name: CHROMOFINE YELLOW 6206EC, available from DAY HI INDUSTRIAL CO., LTD.) were put in a mayonnaise bottle, and subjected to vibration for 1 hour by a pigment vibrator (available from Hitachi Seisaku Co., Ltd.) to preliminarily pulverize the beads, followed by taking out the zirconia beads having a particle diameter of 2.0mm, adding 200 parts by mass of the zirconia beads having a particle diameter of 0.1mm, and similarly subjected to dispersion for 4 hours by a pigment vibrator to preliminarily pulverize the beads to obtain a color material dispersion liquid III-G1.

(2) Production of photosensitive colored resin composition III-G1 for color Filter

To the dispersion liquid III-G111.40 parts by mass obtained in the above (1), 0.64 part by mass of an alkali-soluble resin A solution, 0.60 part by mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toyo Seisaku K.K.), 0.09 part by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name: IRGACURE907, manufactured by BASF K K.K.), 0.04 part by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name: IRGACURE369, manufactured by BASF), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, a fluorine-based surfactant (trade name MEGAFACE F559, manufactured by DIC corporation) 0.07 parts by mass, and PGMEA7.14 parts by mass to obtain a photosensitive colored resin composition III-G1 for a color filter.

(3) Formation of colored layer

The photosensitive colored resin compositions III to G1 obtained in the above (2) were applied to Glass substrates (NH Techno Glass, "NA 35", Inc.) having a thickness of 0.7mm and 100mm X100 mm by using a spin coater, respectively, and then dried at 80 ℃ for 3 minutes by using a hot plate, and irradiated with 60mJ/cm by using an ultra-high pressure mercury lamp²The resultant was post-baked in a dust-free oven at 230 ℃ for 30 minutes to adjust the film thickness so that the chromaticity under C light source was 0.570 and 0.260, thereby forming a colored layer III-G1.

(examples III-2 to III-6 and comparative examples III-CI to III-C5)

(1) Production of colorant Dispersion III-G2-III-G6 and III-CG 1-III-CG 5

In example III-1 (1), color material dispersions III-G2 to III-G6 and III-CG1 to III-CG5 were obtained in the same manner as in example III-1 (1) except that the type and the amount of the dispersant used were changed so that the solid content was the same part by mass instead of the dispersant b solution, the color materials were changed in comparative examples III-C1 to III-C3, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, as shown in Table 13.

(2) Production of photosensitive colored resin compositions III-G2-III-G6 and III-CG 1-III-CG 5 for color Filter

Photosensitive colored resin compositions III-G2 to III-G6 and III-CG1 to III-CG5 for color filters were obtained in the same manner as in (2) of example III-1 except that the color material dispersions III-G2 to III-G6 and III-CG1 to III-CG5 were used in place of the color material dispersion III-G1 in (2) of example III-1, and the amounts of alkali-soluble resins were adjusted so that the P/V ratios were the values shown in Table 13 so that the film thicknesses were 2.35. mu.m, respectively, in examples III-2 to III-6 and comparative examples III-C1 to III-C5.

(3) Formation of colored layer

In example III-1 (3), colored layers III-G2 to III-G6 and III-CG1 to III-CG5 were obtained in the same manner as in example III-1 (3) except that the photosensitive colored resin compositions III-G2 to III-G6 and III-CG1 to III-CG5 were used in place of the photosensitive colored resin composition III-G1, respectively.

Examples III-7 to III-10, III-33)

(1) Production of photosensitive colored resin compositions III-G7-III-G10 and III-33 for color Filter

Photosensitive colored resin compositions III-G7 to III-G8 and III-G33 for color filters were obtained in the same manner as in (2) of example III-1 except that the photoinitiators were changed to those shown in Table 13 in examples III-7 to III-8 and III-33.

In example III-9, the procedure was carried out in the same manner as in (2) in example III-1 except that 0.10 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF corporation) and 0.05 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF) were used instead of 0.02 parts by mass of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) in (2) in example III-1, a photosensitive colored resin composition III-G9 for a color filter was obtained.

In example III-10, a photosensitive colored resin composition III-G10 for a color filter was obtained in the same manner as in (2) of example III-1 except that the solution of alkali-soluble resin A as the alkali-soluble resin was replaced with a solution of alkali-soluble resin B (an epoxy (meth) acrylate resin having a carboxyl group and a Cardo structure, model INR-16M, manufactured by Nagase ChemteX, Ltd.) and the amount of the resin used was adjusted so that the solid content was the same weight.

(3) Formation of colored layer

Colored layers III-G7 to III-G10 and III-G33 were obtained in the same manner as in (3) of example III-1, except that the photosensitive color resin compositions III-G7 to III-G10 and III-G33 were used in place of the photosensitive color resin composition III-G1 in (3) of example III-1.

[ Table 13]

The table is abbreviated as follows.

G36: C.I. pigment Green 36 (trade name: FASTOGEN GREEN 2YK-50, available from DIC corporation)

Y138: pigment YELLOW 138 (trade name: CHROMOFINE YELLOW 6206EC, manufactured by DAHI RIGHS CHEMICAL INDUSTRIAL CO., LTD.)

G58, G7, byk-161, PB822, NCI-831, TR-PBG-304, OXE03 and NCI-930 are the same as in example II series.

(examples III-11 to III-16 and comparative example III-C6)

(1) Production of colorant Dispersion III-G11-III-G16 and III-CG6

In example III-1 (1), color material dispersions III-G11 to III-G16 and III-CG6 were obtained in the same manner as in example III-1 (1), except that the type and the amount of the color material used were changed as shown in Table 14, the amount of the dispersant used was changed so that the solid content was the same parts by mass, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass.

(2) Production of photosensitive colored resin compositions III-G11-III-G16 and III-CG6 for color Filter

Photosensitive colored resin compositions III-G11 to III-G16 and III-CG6 for color filters were obtained in the same manner as in (2) of example III-1 except that the above-mentioned color material dispersions III-G11 to III-G16 and III-CG6 were used in place of the color material dispersion III-G1 in (2) of example III-1, respectively, and the amounts of alkali-soluble resins were adjusted so that the P/V ratios were the values shown in Table 14, respectively, in order to obtain a film thickness of 2.80. mu.m.

(3) Formation of colored layer

Colored layers III-G11 to III-G16 and III-CG6 were obtained in the same manner as in (3) of example III-1 except that the photosensitive colored resin compositions III-G11 to III-G16 and III-CG6 were used in place of the photosensitive colored resin composition III-G1 in (3) of example III-1, respectively. In comparative example III-C6 in which PG58 was used as a color material, the chromaticity of y equal to 0.610 and the chromaticity of x equal to 0.210 under the C light source could not be achieved.

[ Table 14]

The table is abbreviated as follows.

Y150: C.I. pigment yellow 150 (trade name: LEVASCREEN YELLOW G04, manufactured by LANXESS Co., Ltd.)

Ni-azo-1: a pigment (azo pigment with a molar ratio of Ni: Zn ═ 1: 1) which was a derivative of c.i. pigment yellow 150 prepared according to the following preparation example

(preparation example)

To 550g of distilled water were introduced 23.1g of diazobarbituric acid and 19.2g of barbituric acid. Next, azobarbituric acid (0.3 mol) was prepared using an aqueous potassium hydroxide solution, and the mixture was mixed with 750g of distilled water. 5g of 30% hydrochloric acid are added dropwise. Thereafter, 38.7g of melamine were introduced. Then, 0.3 mol of a nickel chloride solution and 0.3 mol of a zinc chloride solution were mixed and added, and the mixture was stirred at 80 ℃ for 8 hours. The pigment was separated by filtration, washed, dried at 120 ℃, and ground with a mortar to obtain a derivative pigment of c.i. pigment yellow 150.

(examples III-17 to III-21 and comparative example III-C7)

Production of colorant Dispersion III-G17-III-G21 and III-CG7

In example III-1 (1), color material dispersions III-G17 to III-G21 and III-CG7 were obtained in the same manner as in example III-1 (1) except that the type and the amount of the color material used were changed, the amount of the dispersant used was changed so that the solid content was the same parts by mass, and the amount of PGMEA was adjusted to 100 parts by mass in total as shown in Table 15.

(2) Production of photosensitive colored resin compositions III-G17-III-G21 and III-CG7 for color Filter

Photosensitive colored resin compositions III-G17 to III-G21 and III-CG7 for color filters were obtained in the same manner as in (2) of example III-1 except that the above-mentioned color material dispersions III-G17 to III-G21 and III-CG7 were used in place of the color material dispersion III-G1 in (2) of example III-1, respectively, and the amounts of alkali-soluble resins were adjusted so that the P/V ratios were the values shown in Table 15, respectively, so as to obtain film thicknesses of 2.80. mu.m.

(3) Formation of colored layer

Colored layers III-G17 to III-G21 and III-CG7 were obtained in the same manner as in (3) of example III-1 except that the photosensitive colored resin compositions III-G17 to III-G21 and III-CG7 were used in place of the photosensitive colored resin composition III-G1 in (3) of example III-1, respectively. In comparative example III-C7 in which PG58 was used as a color material, the chromaticity of y equal to 0.626 and the chromaticity of x equal to 0.205 under the C light source could not be achieved.

[ Table 15]

Watch 15

The table is abbreviated as follows.

Y185: pigment Yellow 185 (trade name: Paliotol (registered trade Mark) Yellow D1155, manufactured by BASF corporation)

(examples III-22 to III-24)

Production of colorant Dispersion III-G22-III-G24

In example III-1 (1), color material dispersions III-G22 to III-G24 were obtained in the same manner as in example III-1 (1), except that the type and the amount of the color material used were changed, the amount of the dispersant used was changed so that the solid content was the same parts by mass, and the amount of PGMEA was adjusted to 100 parts by mass in total as shown in Table 16.

(2) Production of photosensitive colored resin compositions III-G22-III-G24 for color Filter

Photosensitive colored resin compositions III-G22 to III-G24 for color filters were obtained in the same manner as in (2) of example III-1, except that the above-mentioned color material dispersions III-G22 to III-G24 were used in place of the color material dispersion III-G1 in (2) of example III-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were the values shown in Table 16, respectively, in order to adjust the film thickness to 3.30. mu.m.

(3) Formation of colored layer

Colored layers III-G22 to III-G24 were obtained in the same manner as in (3) of example III-1, except that the photosensitive color resin compositions III-G22 to III-G24 were used in place of the photosensitive color resin composition III-G1 in (3) of example III-1.

[ Table 16]

TABLE 16

(examples III-25 to III-27)

Production of colorant Dispersion III-G25-III-G27

In example III-1 (1), color material dispersions III-G25 to III-G27 were obtained in the same manner as in example III-1 (1), except that the type and the amount of the color material used were changed, the amount of the dispersant used was changed so that the solid content was the same parts by mass, and the amount of PGMEA was adjusted to 100 parts by mass in total as shown in Table 17.

(2) Production of photosensitive colored resin compositions III-G25-III-G27 for color Filter

Photosensitive colored resin compositions III-G25 to III-G27 for color filters were obtained in the same manner as in (2) of example III-1, except that the above-mentioned color material dispersions III-G25 to III-G27 were used in place of the color material dispersion III-G1 in (2) of example III-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were the values shown in Table 17, respectively, in order to adjust the film thickness to 3.30. mu.m.

(3) Formation of colored layer

Colored layers III-G25 to III-G27 were obtained in the same manner as in (3) of example III-1, except that the photosensitive color resin compositions III-G25 to III-G27 were used in place of the photosensitive color resin composition III-G1 in (3) of example III-1.

[ Table 17]

TABLE 17

(examples III-28)

(1) Production of color Material Dispersion

6.22 parts by mass of a dispersant b solution as a dispersant, 13 parts by mass of C.I. pigment Green 59(PG59, product name: FASTOGEN GREEN C100 DIC), 14.59 parts by mass of an alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0mm were placed in a mayonnaise bottle, and the bottle was preliminarily pulverized by vibration for 1 hour with a pigment vibrator (manufactured by Kunststoff iron Co., Ltd.), then the zirconia beads having a particle size of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle size of 0.1mm were added, and the mixture was finally pulverized by dispersion for 4 hours with a pigment vibrator to obtain a GREEN color material dispersion g.

6.22 parts by mass of a dispersant b solution as a dispersant, 13 parts by mass of C.I. pigment YELLOW 138(PY138, trade name: CHROMOFINE YELLOW 6206EC, manufactured by DAIGAIJING INDUSTRIAL CO., LTD.) as a color material, 14.59 parts by mass of an alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle size of 2.0mm were put in a mayonnaise bottle, and vibrated for 1 hour by a pigment vibrator (manufactured by Kubotai iron Ltd.) to preliminarily pulverize, then zirconia beads having a particle size of 2.0mm were taken out, 200 parts by mass of zirconia beads having a particle size of 0.1mm were added, and similarly dispersed for 4 hours by a pigment vibrator to preliminarily pulverize, thereby obtaining a YELLOW color material dispersion liquid y.

(2) Production of photosensitive colored resin composition III-G28 for color Filter

4.67 parts by mass of the green colorant dispersion g obtained in the above (1), 6.73 parts by mass of the yellow colorant dispersion y, 0.64 parts by mass of the alkali-soluble resin A solution, 0.60 parts by mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toyo Seisaku Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name: IRGACURE907, manufactured by BASF Co., Ltd.), 0.09 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name: IRGACURE369, manufactured by BASF Co., Ltd.), 0.04 parts by mass of ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, a fluorine-based surfactant (trade name MEGAFACE F559, manufactured by DIC corporation) 0.07 parts by mass, and PGMEA7.14 parts by mass to obtain a photosensitive colored resin composition III-G28 for a color filter.

(3) Formation of colored layer

A colored layer III-G28 was obtained in the same manner as in (3) of example III-1, except that the photosensitive colored resin composition III-G28 was used in place of the photosensitive colored resin composition III-G1 in (3) of example III-1.

The obtained photosensitive colored resin composition III-G28 for a color filter had the same composition as the photosensitive colored resin composition III-G1 for a color filter of example III-1, and the evaluation results of the photosensitive colored resin composition III-G28 for a color filter and the colored layer III-G28 were the same as the evaluation results of the photosensitive colored resin composition III-G1 for a color filter and the colored layer III-G1.

[ evaluation method of example III series ]

The optical performance evaluation, the contrast evaluation, and the display defect evaluation were performed as follows. The evaluation of dispersibility of the color material dispersion, the evaluation of solvent re-solubility, the evaluation of development residue, the evaluation of development adhesion, the evaluation of development resistance, and the evaluation of water bleeding were carried out in the same manner as in example II series.

< evaluation of optical Properties and evaluation of contrast >

The contrast, chromaticity (x, Y) and brightness (Y) of the colored layers obtained in examples and comparative examples were measured using a sakaguchi contrast measuring apparatus CT-1B and an Olympus microscopic spectrophotometer OSP-SP 200.

In comparative example 6 using PG58 as a color material, it was not possible to realize chromaticity values of y equal to 0.610 and x equal to 0.210 under the C light source. In comparative example 7 using PG58 as a color material, chromaticity with y being 0.626 and x being 0.205 under the C light source could not be realized.

(reference for contrast evaluation)

Values when y is 0.570 and x is 0.260 under the C light source

A: over 12000

B：12000～10000

C: less than 10000

< evaluation of display failure >

The colored layers obtained in examples and comparative examples were evaluated for display defects using a dielectric impedance measurement system 126096W (manufactured by eastern Technical).

(evaluation criteria for display failure)

A: a dielectric loss tangent (tan. delta.) at 100Hz of less than 0.023

B: a dielectric loss tangent (tan delta) of 0.023 to 0.048 at 100Hz

C: a dielectric loss tangent (tan. delta.) at 100Hz of more than 0.048

If the evaluation criterion is a or B, it can be used in practice, and if the evaluation result is a, it shows a high effect of suppressing the defect.

[ integration of the results of the series III of examples ]

As is apparent from the results in tables 13 to 17, the viscosity stability of the color material dispersions of the examples in which PG59 and a yellow color material are combined with a dispersant which is a polymer having a constituent unit represented by the general formula (I) is good. On the other hand, the viscosity stability of the color material dispersions of comparative examples III-C4 to III-C5, in which PG59 was combined with a urethane-based dispersant or a polyester-based dispersant, was remarkably deteriorated. The color material dispersions of comparative examples III-C1, III-C2 and III-C3, in which PG58, PG7 and PG36 were combined with a dispersant which is a polymer having a constituent unit represented by the general formula (I), were significantly inferior in viscosity stability to those of example III-1. Furthermore, the dispersion medium liquids of comparative examples III-C2 and III-C3, in which PG7 and PG36 were combined with a dispersant which is a polymer having a constituent unit represented by the general formula (I), were inferior in dispersibility.

As is apparent from table 13, the photosensitive colored resin compositions for color filters of examples III-1 to III-10, in which PG59 was combined with the yellow color material PY138 and a dispersant which is a polymer having a constituent unit represented by general formula (I), showed a region where x was 0.260 and suppressed the occurrence of display defects and formed colored layers with high luminance when y was 0.570. It is also apparent that the photosensitive colored resin compositions for color filters of examples III-1 to III-10, in which PG59 contains the yellow coloring material PY138 and a dispersant which is a polymer having a constitutional unit represented by the general formula (I), have good color material dispersion stability, excellent contrast, excellent solvent re-solubility, and suppressed development residue.

Wherein a block copolymer comprising an A block comprising a constituent unit represented by the above general formula (I) and a B block comprising a constituent unit derived from a carboxyl group-containing monomer and having solventropic properties is used as a dispersant; or a salt-type block copolymer which forms a salt with at least a part of the nitrogen site of the constituent unit represented by the general formula (I), wherein the acid value of the dispersant is 1mgKOH/g or more and 18mgKOH/g or less, and the glass transition temperature of the dispersant is 30 ℃ or more, particularly, development residue generation is suppressed, and development adhesion is excellent in examples III-1, III-2, III-6 to III-10, and III-33. Further, example III-10, which used an epoxy (meth) acrylate resin having a carboxyl group and containing a Cardo structure as an alkali-soluble resin in a photosensitive colored resin composition, was superior to example III-1 in terms of development adhesion, development resistance and water bleeding occurrence-inhibiting effect.

In addition, in the examples, it is apparent from the comparison among examples III-1, III-7, III-8, III-9 and III-33 that the examples using the oxime ester type photoinitiator as the photoinitiator have higher development resistance and higher effect of inhibiting the occurrence of water bleeding.

As is apparent from tables 14 and 15, when PG59 is combined with a yellow color material and a dispersant which is a polymer having a constituent unit represented by general formula (I), the color gamut is increased, and even when y is 0.570 to 0.626, a chromaticity region where x is 0.205 to 0.324 can be displayed, and furthermore, a chromaticity region where y is 0.659 can be displayed, and the occurrence of display defects is suppressed, and a colored layer with high luminance can be formed.

In example III-23 in table 16, when PG59 and the yellow color material were further combined with PG58, the above-mentioned P/V ratio was significantly reduced and the luminance was further improved as compared with example III-22 in which PG59 was used alone as the green color material. In examples III to 24, when PG59 and PG58 as green color materials and PY138 and PY150 as yellow color materials were combined, it was found that the above P/V ratio could be further lowered.

In examples III to 26 in table 17, when PG59 and a yellow color material were further combined with PG7, the above-described P/V ratio could be significantly reduced, and the luminance could be also improved. In examples III to 27, when PY138 and PY150 as yellow color materials were combined with PG59 and PG7 as green color materials, the above-mentioned P/V ratio could be further significantly lowered.

On the other hand, when PG58 is used as in comparative example III-C1, when y is 0.570, although a region where x is 0.260 can be displayed, a display failure occurs, and the luminance is inferior to that in the case of PG 59. In addition, development residue is also deteriorated. When PG7 and PG36 are used as in comparative examples III-C2 and III-C3, a region where x is 0.260 can be displayed when y is 0.570, but the luminance is low. Further, even when a dispersant which is a polymer having a constituent unit represented by the general formula (I) is used in combination, the dispersibility is deteriorated, and therefore, the contrast is low, and the re-solubility and the residue are also deteriorated.

On the other hand, the photosensitive colored resin compositions for color filters of comparative examples III-C4 to III-C5, in which PG59 was combined with a urethane-based dispersant and a polyester-based dispersant, had lower brightness, lower contrast, and deteriorated resolubility and residue, compared to the examples, because of the deteriorated dispersibility.

Example IV series: third aspect of the second aspect of the present invention

In the example IV system, the solutions of dispersants a to h were obtained in the same manner as in Synthesis examples II-1 to II-8 of the example II series, respectively. The alkali-soluble resin A solution was obtained in the same manner as in Synthesis example II-9 of example II series.

(example IV-1)

(1) Production of color Material Dispersion IV-G1

6.22 parts by mass of a dispersant b solution as a dispersant, 6.42 parts by mass of C.I. pigment Green 59(PG59, trade name: FASTOGEN GREEN C100, manufactured by DIC corporation) as a coloring material, 1.39 parts by mass of C.I. pigment BLUE 15:4(PB15:4, trade name: CYANINE BLUE CP-1, manufactured by DAIGAIJING INDUSTRIAL CO., LTD.), 1.40 parts by mass of C.I. pigment YELLOW 139(PY139, trade name: IRGAPHOR YELLOW 2R-CF, manufactured by BASF) as a YELLOW coloring material, 3.80 parts by mass of C.I. pigment YELLOW 150(PY150, trade name: LEVASCREEN YELLOW G04, manufactured by LAXESS corporation), 14.59 parts by mass of an alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, 100 parts by mass of zirconium oxide beads having a particle size of 2.0mm, 1.0 part by mass of zirconium oxide beads having a particle size of 2.0mm, 100 parts by mass of zirconium oxide beads having a particle size, which were put in a mayonnais bottle, pulverized with a pigment vibrator (zirconium vibrator, and then added to the bottle, and then, the resultant mixture was taken out, and the mixture was stirred, similarly, the pigment dispersion was dispersed for 4 hours by a pigment shaker to obtain a colorant dispersion IV-G1.

(2) Production of photosensitive colored resin composition IV-G1 for color Filter

To the dispersion liquid IV-G111.41 parts by mass obtained in the above (1), 2.75 parts by mass of an alkali-soluble resin A solution, 0.60 parts by mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toyo Seisaku K.K.), 0.09 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name: IRGACURE907, manufactured by BASF K K.K.), 0.04 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name: IRGACURE369, manufactured by BASF), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, a fluorine-based surfactant (trade name MEGAFACE F559, manufactured by DIC corporation) 0.07 parts by mass, and PGMEA 9.72 parts by mass to obtain a photosensitive colored resin composition IV-G1 for a color filter.

(3) Formation of colored layer

The photosensitive colored resin compositions IV to G1 obtained in the above (2) were applied to Glass substrates (NH Techno Glass, "NA 35", Inc.) having a thickness of 0.7mm and 100mm X100 mm by using a spin coater, respectively, and then dried at 80 ℃ for 3 minutes by using a hot plate, and irradiated with 60mJ/cm by using an ultra-high pressure mercury lamp²The resultant was post-baked in a dust-free oven at 230 ℃ for 30 minutes, and the thickness of the cured film was adjusted to 2.80 μm to form a colored layer IV-G1.

(examples IV-2 to IV-6, IV-11 to IV-13, comparative examples IV-C1 to IV-C4)

(1) Production of colorant Dispersion IV-G2-IV-G6, IV-G11-IV-G13, and IV-CG 1-IV-CG 4

In examples IV-2 to IV-6 and comparative examples IV-C3 to IV-C4, color material dispersion liquids IV-G2 to IV-G6 and IV-CG3 to IV-CG4 were obtained in the same manner as in (1) of example IV-1, except that the kind and the amount of the dispersant used were changed so that the solid content was the same parts by mass and the amount of PGMEA was adjusted to 100 parts by mass in total in (1) of example IV-1, as shown in Table 18. In examples IV-11 to IV-13, dispersion liquids IV-G11 to IV-G13 were obtained in the same manner as in (1) of example IV-1 except that the amount of PGMEA was adjusted to 100 parts by mass in total by changing the color material in (1) of example IV-1. In comparative examples IV-C1 to IV-C2, IV-CG1 to IV-CG2 were obtained in the same manner as in (1) in example IV-1, except that in (1) in example IV-1, a solution of dispersant a was used in place of a solution of dispersant b, and the color material was changed.

(2) Production of photosensitive colored resin compositions IV-G2-IV-G6, IV-G11-IV-G13, and IV-CG 1-IV-CG 4 for color Filter

Photosensitive colored resin compositions IV-G2 to IV-G6, IV-G11 to IV-G13 and IV-1 to IV-CG4 for color filters were obtained in the same manner as in (2) of example IV-1 except that the above-mentioned color material dispersions IV-G2 to IV-G6, IV-G11 to IV-G13 and IV-CG1 to IV-CG4 were used in place of the color material dispersion IV-G1 in (2) of example IV-1, respectively, and the amount of alkali-soluble resin was adjusted so that the above-mentioned P/V ratio became 2.8. mu.m.

(3) Formation of colored layer

The same procedures as in (3) of example IV-1 were carried out except that in (3) of example IV-1, instead of the photosensitive colored resin composition IV-G1, the photosensitive colored resin compositions IV-G2 to IV-G6, IV-G11 to IV-G13 and IV-CG1 to IV-CG4 were used, respectively, to obtain colored layers IV-G2 to IV-G6, IV-G11 to IV-G13 and IV-CG1 to IV-CG 4.

(examples IV-7 to IV-10, IV-36)

(1) Production of photosensitive colored resin compositions IV-G7-IV-G10 and IV-G36 for color Filter

Photosensitive colored resin compositions IV-G7 to IV-G8 and IV-G36 for color filters were obtained in the same manner as in (2) of example IV-1 except that the photoinitiators were changed to those shown in Table 18 in examples IV-7 to IV-8 and IV-36.

In addition, in example IV-9, the procedure was carried out in the same manner as in (2) in example IV-1 except that 0.10 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF corporation) and 0.05 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF) were used instead of 0.02 parts by mass of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime) in (2) in example IV-1, a photosensitive colored resin composition IV-G9 for a color filter was obtained.

In example IV-10, a photosensitive colored resin composition IV-G10 for a color filter was obtained in the same manner as in (2) of example IV-1 except that the alkali-soluble resin solution A was replaced with an alkali-soluble resin solution B (an epoxy (meth) acrylate resin having a carboxyl group and a Cardo structure, model INR-16M, manufactured by Nagase ChemteX, Ltd.) and the amount of the resin used was adjusted so that the solid content was the same weight.

(3) Formation of colored layer

The same procedures as in (3) of example IV-1 were carried out except that in (3) of example IV-1, instead of the photosensitive colored resin composition IV-G1, the photosensitive colored resin compositions IV-G7 to IV-G10 and IV-G36 were used, respectively, to obtain colored layers IV-G7 to IV-G10 and IV-G36.

[ Table 18]

Here, each in the table is abbreviated as follows.

PB15: 4: pigment BLUE 15:4 (trade name: cyanone BLUE CP-1, manufactured by Dai Nissan chemical industries Co., Ltd.)

PB15: 3: pigment BLUE 15:3 (trade name: CHROMOFINE BLUE A-220JC, manufactured by Dari refining industries Co., Ltd.)

Note that G36, G58, Ni-azo-1, Y138, byk-161, PB822, NCI-831, TR-PBG-304, OXE03, NCI-930 are the same as in example II or III series.

(examples IV-14 to IV-15 and comparative examples IV-C5 to IV-C10)

(1) Production of colorant Dispersion IV-G14-IV-G15 and IV-CG 5-IV-CG 10

In example IV-1 (1), color material dispersion liquids IV-G14 to IV-G15 and IV-CG5 to IV-CG10 were obtained in the same manner as in example IV-1 (1), except that the type and the amount of the color material used were changed as shown in Table 19, the amount of the dispersant used was changed so that the solid content was the same parts by mass, and the amount of PGMEA was adjusted to 100 parts by mass in total in example IV-1 (1).

(2) Production of photosensitive colored resin compositions IV-G14-IV-G15 and IV-CG 5-IV-CG 10 for color Filter

Photosensitive colored resin compositions IV-G14 to IV-G15 and IV-CG6 for color filters were obtained in the same manner as in (2) of example IV-1 except that the above-mentioned color material dispersions IV-G14 to IV-G15 and IV-CG6 were used in place of the color material dispersion IV-G1 in (2) of example IV-1, respectively, and the amount of alkali-soluble resin was adjusted so that the P/V ratios were the values shown in Table 19, respectively, so as to obtain film thicknesses of 2.8. mu.m.

In the combinations of the color materials of comparative example IV-C5 and comparative examples IV-C7 to IV-C10, it was not possible to prepare a photosensitive colored resin composition having a film thickness of 2.8 μm and capable of realizing chromaticities of x equal to 0.200 and y equal to 0.710.

(3) Formation of colored layer

In example IV-1 (3), colored layers IV-G14 to IV-G15 and IV-CG6 were obtained in the same manner as in example IV-1 (3) except that the photosensitive colored resin compositions IV-G14 to IV-G15 and IV-CG6 were used in place of the photosensitive colored resin composition IV-G1, respectively.

[ Table 19]

PB15: 6: C.I. pigment BLUE 15:6 (trade name FASTOGEN BLUE A510, manufactured by DIC Ltd.)

(examples IV-16 to IV-30)

Production of colorant Dispersion IV-G16-IV-G30

In example IV-1 (1), color material dispersion liquids IV-G16 to IV-G30 were obtained in the same manner as in example IV-1 (1), except that the type and the amount of the color material used were changed, the amount of the dispersant used was changed so that the solid content was the same parts by mass, and the amount of PGMEA was adjusted to 100 parts by mass in total as shown in Table 20.

(2) Production of photosensitive colored resin compositions IV-G16-IV-G30 for color Filter

Photosensitive colored resin compositions IV-G16 to IV-G30 for color filters were obtained in the same manner as in (2) of example IV-1, except that the above-mentioned color material dispersions IV-G16 to IV-G30 were used in place of the color material dispersion IV-G1 in (2) of example IV-1, and the amounts of the alkali-soluble resins were adjusted so that the P/V ratios were the values shown in Table 20, respectively, in order to adjust the film thickness to 2.8. mu.m.

(3) Formation of colored layer

In the same manner as in (3) of example IV-1 except that the photosensitive colored resin compositions IV-G16 to IV-G30 were used in place of the photosensitive colored resin composition IV-G1 in (3) of example IV-1, colored layers IV-G16 to IV-G30 were obtained.

[ Table 20]

G7 and Y185 are the same as those of example III series.

(example IV-35)

(1) Production of color Material Dispersion

The same procedure as in the GREEN color material dispersion g was carried out except that 13 parts by mass of c.i. pigment BLUE 15:4(PB15:4, trade name: cyanomine BLUE CP-1, manufactured by dais chemical industries, ltd.) was used as the color material in place of 13 parts by mass of c.i. pigment GREEN 59(PG59, trade name: FASTOGEN GREEN C100, manufactured by DIC corporation) as the color material to obtain a BLUE color material dispersion b.

The same procedure as for the GREEN color material dispersion g was carried out except that 13 parts by mass of C.I. pigment YELLOW 139(PY139, trade name: IRGAPHOR YELLOW 2R-CF, manufactured by BASF) was used as the color material in place of 13 parts by mass of C.I. pigment GREEN 59(PG59, trade name: FASTOGEN GREEN C100 DIC, Inc.) as the color material in the GREEN color material dispersion g, to obtain a YELLOW color material dispersion y 1.

The same procedure as in the GREEN color material dispersion g was carried out except that 13 parts by mass of c.i. pigment yellow 150(PY150, trade name: LEVASCREEN YELLOW G04, manufactured by LAXESS corporation) was used as the color material in place of 13 parts by mass of c.i. pigment GREEN 59(PG59, manufactured by FASTOGEN GREEN C100 DIC), which was the color material, to obtain a yellow color material dispersion y 2.

(2) Production of photosensitive colored resin composition IV-G35 for color Filter

5.63 parts by mass of the green color material dispersion g obtained in the above-mentioned (1), 1.22 parts by mass of the blue color material dispersion b, 11.23 parts by mass of the yellow color material dispersion y 23.33 parts by mass of the yellow color material dispersion y, 2.75 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 9, 0.60 parts by mass of a polyfunctional monomer (trade name ARONIX M-403, manufactured by Toyo Synthesis Ltd.), 0.09 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF Co., Ltd.), 0.09 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF Co., Ltd.), 0.04 parts by mass of ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole (O-3-yl) -, 1- (O-acetyloxime) (photoinitiator: trade name: ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, a fluorine-based surfactant (trade name: MEGAFACE F559, manufactured by DIC corporation) 0.07 parts by mass, and PGMEA 9.72 parts by mass to obtain a photosensitive colored resin composition IV-G35 for a color filter.

(3) Formation of colored layer

A colored layer IV-G35 was obtained in the same manner as in (3) of example IV-1, except that the photosensitive colored resin composition IV-G35 was used in place of the photosensitive colored resin composition IV-G1 in (3) of example IV-1.

The obtained photosensitive colored resin composition IV-G35 for a color filter had the same composition as the photosensitive colored resin composition IV-G1 for a color filter of example IV-1, and the evaluation results of the photosensitive colored resin composition IV-G35 for a color filter and the colored layer IV-G35 were the same as the evaluation results of the photosensitive colored resin composition IV-G1 for a color filter and the colored layer IV-G1.

[ evaluation method of example IV series ]

The optical performance evaluation and the contrast evaluation were performed as follows. Evaluation of dispersibility of the color material dispersion liquid, evaluation of display defect, evaluation of solvent re-solubility, evaluation of development residue, evaluation of development adhesion, evaluation of development resistance, and evaluation of water bleeding were carried out in the same manner as in the example II series.

< evaluation of optical Properties and evaluation of contrast >

(reference for contrast evaluation)

The values of C illuminant when y is 0.670 and x is 0.210

A: over 8000

B：6000～8000

C: less than 6000

[ integration of results for the example IV System ]

As is apparent from the results in tables 18 to 20, the viscosity stability of the color material dispersion liquid of the example in which PG59, the blue color material, and the specific yellow color material are combined with the dispersant which is the polymer having the constituent unit represented by the general formula (I) is good. On the other hand, the colorant dispersions of comparative examples IV-C3 to IV-C4, in which PG59 was combined with a urethane dispersant and a polyester dispersant, were significantly deteriorated in viscosity stability. The color material dispersions of comparative examples IV-C1 and IV-C2, in which PG58 and PG36 were combined with a dispersant which is a polymer having a constituent unit represented by the general formula (I), were significantly inferior in viscosity stability to those of example IV-1. Furthermore, the dispersibility of the colorant dispersion liquid of comparative examples IV-C2, in which PG36 was combined with a dispersant which is a polymer having a constituent unit represented by the general formula (I), was deteriorated.

As is apparent from table 18, the photosensitive colored resin compositions for color filters of examples IV-1 to IV-13 and IV-36, in which the blue color material, the specific yellow color material, and the dispersant which is a polymer having a constituent unit represented by general formula (I) were combined in PG59, showed a region where x was 0.210 when y was 0.670, suppressed the occurrence of display defects, and formed colored layers with high luminance. The photosensitive colored resin compositions for color filters of examples IV-1 to IV-13 and IV-36 were excellent in the dispersion stability of the coloring material, the contrast, and the solvent re-solubility, and further, the occurrence of development residue was suppressed.

Among them, it is clear that when a block copolymer comprising an A block comprising a constituent unit represented by the above general formula (I) and a B block comprising a constituent unit derived from a carboxyl group-containing monomer and having solventropic properties is used as a dispersant; or a salt-type block copolymer which forms a salt with at least a part of the nitrogen site of the constituent unit represented by the general formula (I), particularly suppresses development residue and is excellent in development adhesion (examples IV-1, IV-2, IV-6 to IV-13 and IV-36 having the same P/V ratio), wherein the acid value of the dispersant is 1mgKOH/g or more and 18mgKOH/g or less, and the glass transition temperature of the dispersant is 30 ℃ or more.

Further, example IV-10, which used an epoxy (meth) acrylate resin having a carboxyl group containing a Cardo structure as an alkali-soluble resin in the photosensitive colored resin composition, was superior to example IV-1 in terms of development adhesion, development resistance and water bleeding occurrence-inhibiting effect.

In the examples, it is apparent from the comparison among examples IV-1, IV-7, IV-8, IV-9 and IV-36 that the development resistance and the effect of inhibiting the occurrence of water bleed are improved in the examples using the oxime ester photoinitiator as the photoinitiator.

As is apparent from tables 19 and 20, when a blue color material and the specific yellow color material are combined in PG59 as a dispersant of a polymer having a structural unit represented by general formula (I), the color gamut is increased, and even when y is 0.570 to 0.720, a chromaticity region where x is 0.140 to 0.265 can be displayed, and furthermore, a chromaticity region where y is 0.750 can be displayed, and the occurrence of display defects is suppressed, and a colored layer having a higher luminance than conventional can be formed.

In examples IV to 29 in table 20, when a blue color material and the specific yellow color material are combined with PG59 and PG7 is further combined, the above-mentioned P/V ratio is remarkably decreased and the luminance is also improved as compared with examples IV to 28 in which the same color tone is realized.

On the other hand, as shown in comparative example IV-C1, even if a blue color material and a specific yellow color material were combined as in the examples, when PG58 was used, a region where x was 0.210 could be displayed when y was 0.670, but display failure occurred and the luminance was inferior to that in the case of PG 59. In addition, development residue and development adhesion are also deteriorated. As shown in comparative example IV-C2, even when a blue color material and a specific yellow color material were combined as in the examples, if PG36 was used, a region where x was 0.210 could be displayed when y was 0.670, but display failure occurred and the luminance was low. Further, even when a dispersant which is a polymer having a constituent unit represented by the general formula (I) is used in combination, the dispersibility is not good, and therefore, the contrast is low, and the resolubility, the development residue, and the development adhesion are deteriorated.

On the other hand, the photosensitive colored resin compositions for color filters of comparative examples IV-C3 to IV-C4, in which PG59 was combined with a blue color material and a specific yellow color material, and further with a urethane dispersant and a polyester dispersant, had lower brightness than those of the examples due to the deteriorated dispersibility, lower contrast, and deteriorated resolubility and development residue.

As shown in comparative examples IV-C5, IV-C7, and IV-C10 in table 19, it was not possible to prepare a photosensitive colored resin composition having a film thickness of 2.8 μm and capable of realizing a chromaticity where x is 0.200 and y is 0.710 in a composition using G58 in combination with a yellow color material without combining a blue color material. In addition, it was not possible to prepare a photosensitive colored resin composition having a film thickness of 2.8 μm and capable of realizing chromaticity values of x 0.200 and y 0.710 in the combination of the color materials of comparative examples IV-C8 and IV-C9.

As shown in comparative example IV-C6, when the green color material was not used and the blue color material and the yellow color material were combined, the chromaticity was achieved at a film thickness of 2.8 μm, x was 0.200, and y was 0.710, and no display failure occurred, but the luminance of comparative example IV-C6, which contains a large amount of the blue color material, was significantly deteriorated to such an extent that it could not reach a practical level.

Description of the symbols

1 transparent substrate

2 light-shielding part

3 coloured layer

10 color filter

20 opposed 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 luminescent layer

75 electron injection layer

76 cathode

80 organic light-emitting body

100 organic light emitting display device

Claims

1. A color material dispersion liquid for a color filter, which is a color material dispersion liquid containing a color material, a dispersant and a solvent;

in the general formula (I), R¹Represents a hydrogen atom or a methyl group, A represents a 2-valent linking group, R²And R³Each independently represents a hydrogen atom or a hydrocarbon group which may contain a hetero atom, R²And R³May be bonded to each other to form a ring structure;

in the general formula (1), R^aRepresents a C1-20 linear, branched or cyclic alkyl group, a vinyl group, a phenyl or benzyl group which may have a substituent, or-O-R^e，R^eA linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms; in the general formula (2), R^b、R^b′And R^b″Each independently represents a hydrogen atom, an acidic group or an ester group thereof, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a linear, branched or cyclic alkyl group having a substituentA substituted vinyl group, a phenyl or benzyl group which may have a substituent, or-O-R^f，R^fRepresents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom or an iodine atom; in the general formula (3), R^cAnd R^dEach independently represents a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or-O-R^e，R^eA linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a (meth) acryloyl group connected via an alkylene group having 1 to 4 carbon atoms; wherein R is^cAnd R^dContains carbon atoms.

2. The color material dispersion liquid for a color filter according to claim 1, wherein the block copolymer (P1) in the dispersant contains a constituent unit derived from a hydroxyl group-containing monomer.

3. The color material dispersion liquid for a color filter according to claim 1, wherein the block copolymer (P1) in the dispersion liquid contains at least 1 of:

(i) a constituent unit derived from a hydroxyl group-containing monomer and a constituent unit derived from an aromatic group-containing monomer; and

(ii) a constituent unit derived from a monomer containing a hydroxyl group and an aromatic group.

4. The color material dispersion liquid for a color filter according to claim 1, wherein the salt-type block copolymer contains 0.1 to 0.7 mol of 1 or more compounds selected from the group consisting of the compounds represented by the general formulae (1) to (3) per 1 mol of a nitrogen site at an end of the constituent unit represented by the general formula (I).

5. The color material dispersion liquid for a color filter according to claim 1, wherein the color material contains c.i. pigment green 59.

6. A photosensitive colored resin composition for a color filter, comprising the color material dispersion according to claim 1, an alkali-soluble resin, a polyfunctional monomer and a photoinitiator.

7. The photosensitive colored resin composition for a color filter according to claim 6, wherein the photoinitiator comprises an oxime ester photoinitiator.

8. A color filter comprising at least a transparent substrate and colored layers provided on the transparent substrate, wherein at least one of the colored layers is formed by curing the photosensitive colored resin composition for a color filter according to claim 6.

9. A liquid crystal display device comprising the color filter according to claim 8, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

10. An organic light-emitting display device comprising the color filter according to claim 8 and an organic light-emitting body.