TW201631051A - Color material dispersion liquid for color filters, photosensitive color resin composition for color filters, color filter, liquid crystal display device, and organic light-emitting display device - Google Patents

Abstract

The present invention is to provide a color material dispersion liquid which has excellent color material dispersion stability and which is able to produce a photosensitive color resin composition having excellent adhesion in development and resolubility in solvents, with inhibiting generation of development residues. Disclosed is a color material dispersion liquid for color filters, wherein the color material dispersion liquid contains a color material, a dispersant and a solvent; the dispersant is at least one selected from the group consisting of a block copolymer (P1) and a salt-type block copolymer (P2), the block copolymer (P1) being a block copolymer which includes a block A including at least one constitutional unit represented by the following general formula (I) and a block B including at least one constitutional unit derived from a carboxy group-containing monomer, and the salt-type block copolymer (P2) being a salt-type block copolymer in which at least part of nitrogen sites at terminals of the constitutional units represented by the general formula (I) of the block copolymer and one or more compounds selected from the group consisting of compounds represented by the following general formulae (1) to (3) form salts; and wherein the dispersant has an acid value of 1 to 18 mgKOH/g and a glass transition temperature of 30 DEG C or more: General Formula (I) (symbols in the formulae are as described in the Description.).

Description

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

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

In recent years, with the development of personal computers, especially the development of portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) has also increased, and the market for liquid crystal displays has been expanding. In addition, an organic light-emitting display device similar to an organic EL display having high visibility by self-luminescence has recently attracted attention as a next-generation image display device. In view of the performance of such image display devices, it is strongly desired to further improve image quality or power consumption, such as improvement in contrast or color reproducibility.

Conventional display devices are mostly based on sRGB (IEC61966-2-1) of the international standard specification of color space. However, in order to require a performance closer to the real thing and to further improve the color reproducibility, there is an increasing demand for a display device corresponding to Adobe RGB having a wider color reproduction domain than sRGB. The AdobeRGB specification is defined by the color space advocated by Adobe Systems. In AdobeRGB, the three primary colors are as follows. Determined by the chromaticity coordinates x and y in the XYZ color system. The Adobe RGB specification is characterized by a wider color reproduction domain in the green direction than the sRGB specification.

Red: x=0.64; y=0.34

Green: x=0.21; y=0.71

Blue: x=0.15; y=0.06

In addition, there is also a requirement for a DCI (Digital Cinema Initiatives) specification that conforms to a wider color reproduction domain than sRGB in the red and green directions.

A color filter is used for such a liquid crystal display device or an organic light-emitting display device. For example, the color image of the liquid crystal display device is formed by directly coloring the light passing through the color filter to the color of each pixel constituting the color filter, and synthesizing the color lights to form a color image. As the light source at this time, in addition to the conventional cold cathode ray tube, there are cases where an organic light emitting element of white light emission or an inorganic light emitting element of white light is used. Further, in the organic light-emitting display device, a color filter is used for color adjustment or the like.

In this case, expectations for high luminance, high contrast, and improved color reproducibility in color filters are also increasing.

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

As a method of forming a pixel in a color filter, a pigment dispersion method having an average superior characteristic is widely used from the viewpoints of spectral characteristics, durability, pattern shape, and precision.

In the color filter having the pixel formed by the pigment dispersion method, in order to achieve high luminance or high contrast, the fineness of the pigment is reviewed. By making the pigment subtle It is considered that the scattering of light penetrating the color filter caused by the pigment particles can be reduced to achieve high luminance or high contrast.

However, since the finely divided pigment particles are easily aggregated, there is a problem that the dispersibility or the dispersion stability is lowered.

As a method of improving the dispersion method of the finely divided pigment, it is known to use a dispersant. For example, Patent Document 1 aims to provide a coloring composition for a color filter which is excellent in chromaticity characteristics, developability, and storage stability, and discloses coloring for color filters using a block copolymer as a pigment dispersant. a composition, the block copolymerization system having: an A block having a specific repeating unit having an amine group or an ammonium salt group; and a specific repeating unit having an alkylene oxide chain in a portion containing an alcohol derived from a carboxylate; The B block of the repeating unit of the acidic group.

Further, Patent Document 2 aims to provide a coloring composition for a color filter which is excellent in chromaticity characteristics, developability, and storage stability, and discloses a coloring composition for a color filter using a copolymer as a pigment dispersant. The copolymerization system comprises: a specific repeating unit having an amine group or an ammonium salt group, a repeating unit containing a carboxylate, a repeating unit having an acidic group, and a repeating unit containing a carboxylate as 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 area connecting the three points of the red, green, and blue pixels becomes the limit of the reproducible color. That is, the larger the color of the triangle obtained by the three points of the red, green, and blue pixels, the wider the range of colors that the display device can reproduce on the screen.

In order to achieve the above-mentioned color space of a wide color reproduction domain such as AdobeRGB or DCI, it is particularly required to use the green color of the color filter as the green color of the high color density {(x=0.14~0.30, y=0.55~0.75). More preferably (x=0.14~0.30, y=0.57~0.75), A better area (x=0.14~0.30, y=0.61~0.75)}.

For example, CI green pigment (CIPigment Green) 7 (hereinafter sometimes abbreviated as PG7), CI pigment green 36 (hereinafter sometimes abbreviated as PG36), and CI pigment are exemplified as the green pigment which is widely used as a green pixel. Green 58 (hereinafter sometimes referred to as PG58).

However, when green pixels are produced in such a manner that PG7 is used to achieve the greenness region of the above-described high color density, there is a problem that the luminance of the green pixels is lowered. When PG7 is used as the main green color material to form a green pixel, it becomes a dark color filter.

Further, when green pixels are produced in such a manner that PG36 is used to achieve the above-described high color density green region, although it is not as severe as PG7, there is a problem that the luminance of the green pixels is lowered.

Further, when PG58 is used, although the luminance is high, when the green pixel including the high-density green region is produced, it is necessary to make the green pixel very thick, which is not only problematic in mass production, but only green. Since the pigment is thickened, it is difficult to maintain the performance of the color filter. Further, even if only PG58 is used, there is still a region that cannot be achieved in the green region of the high color density, and there is a limit in producing green pixels in such a manner as to become a larger triangle.

Patent Document 3 describes a colored resin composition for a color filter which can achieve a high chroma green color target chromaticity without requiring thick film formation, and can form a high-intensity green pixel. Pigment of cyanine. However, higher brightness is still required.

On the other hand, the patent document 4 is intended to provide a colored curable resin composition for a color filter which is capable of suppressing the occurrence of a foreign matter failure caused by a zinc bromide phthalocyanine pigment which has been attracting attention as a green pixel in recent years. Revealing a color filter a light-coloring composition which is used in combination as a pigment dispersant as a pigment dispersant containing an amine-based polymer of a specific structural unit, and as a building block having a 4-stage ammonium salt group in a side chain as an aggregation preventing agent, and a 4-grade ammonium An aggregation preventing agent for a block copolymer of a structural unit of a salt base. 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 liquid exhibiting blueish green color and high luminance cannot be obtained.

Moreover, there is a problem that green pixels are prone to display failure. More specifically, the horizontal electric field type liquid crystal display device has a coloring layer of a color filter in the liquid crystal driving electric field, and is greatly affected by the electrical characteristics of the colored layer. When the PG36 is used for the green pixel, in the liquid crystal display device of the horizontal electric field type, various display defects such as liquid crystal alignment disorder due to electrical characteristics of the green pixel and burn-in phenomenon due to the threshold value of switching are generated. . Such display failure is caused by the fact that the green pixel uses PG58, which causes a more significant problem.

In Patent Document 5, in the liquid crystal display device of the horizontal electric field type, the electrical properties of the color layer as the color filter do not adversely affect the switching performance of the liquid crystal, and sufficient performance can be ensured even without providing a protective layer of a transparent resin. Further, as a color filter capable of responding to high color reproducibility, it is revealed that the color layer forming the green pixel contains a specific amount or less of PG36 and has a specific dielectric positive (tan δ) value.

However, in the technique disclosed in Patent Document 5, even if the display defect is reduced, the luminance is insufficient, and it is insufficient in terms of wide color reproducibility.

On the other hand, in Patent Document 6, the green composition for a color filter which can adjust the luminance without lowering the high contrast is disclosed to contain PG58 and a yellow organic pigment, and is selected from the group consisting of blue pigment, red pigment, and purple. A green composition of any of pigments and orange pigments.

However, the technique disclosed in Patent Document 6 is not sufficient in terms of broad color reproducibility.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2011-237769

Patent Document 2: Japanese Patent Laid-Open Publication No. 2012-32767

Patent Document 3: Japanese Patent Laid-Open Publication No. 2013-20558

Patent Document 4: Japanese Patent Laid-Open Publication No. 2012-108266

Patent Document 5: Japanese Patent Laid-Open Publication No. 2009-162979

Patent Document 6: Japanese Patent Laid-Open No. 2011-118051

Among the color filters of recent years, various techniques for mass production of color filters have to be solved in conjunction with techniques for improving the dispersibility of color materials for achieving high luminance or high contrast. That is, in order to increase the concentration of the color material in the resin composition, it is inevitable that the dispersant must be added to cause problems such as occurrence of development residue or delay in development time. Further, when the concentration of the color material is increased and the content of the dispersant is increased, the amount of the adhesive is relatively reduced, so that the problem that the colored resin layer is easily peeled off from the base substrate during development is caused. Therefore, although it is required to have high development adhesiveness as a colored resin composition, there is a problem that the practical level is not reached. Further, in the production step of the color filter, the solid content of the once dried colored resin composition is required to be re-dissolved in a solvent, and is excellent in resolubility to a solvent. For example, when a photosensitive colored resin composition adheres to the tip end of the lip when applying by a die coater, a cured product is formed by drying, and the coating is reopened. When the cured product is not easily dissolved in the photosensitive colored resin composition, the cured product on the lip is partially peeled off, and it tends to adhere to the colored layer of the color filter, which is a cause of foreign matter defects. In particular, when the color material concentration of the colored resin composition is increased, there is a problem that the solvent resolubility is likely to be insufficient, and the yield due to the generation of the foreign matter in the production step of the color filter is lowered.

However, according to the methods described in Patent Documents 1 to 2, in addition to the dispersibility of the color material, various problems in the mass production of the color filter, the occurrence of development residue, development adhesiveness, and solvent resolubility are as follows. It is difficult to solve the same as shown in the comparative example described later.

The present invention has been made in view of the above-mentioned facts, and a first object of the present invention is to provide a color material dispersion of a photosensitive colored resin composition which is excellent in dispersion stability of a color material and which can suppress development residue and which is excellent in development adhesiveness and solvent resolubility. Liquid; a color-sensitive resin composition for color filters for superior color material dispersion, which is excellent in dispersing stability of color materials, which is excellent in development adhesiveness and solvent resolubility, and which can form a comparatively superior colored layer; A color filter formed of a photosensitive colored resin composition for a light sheet; and a liquid crystal display device and an organic light-emitting display device excellent in display characteristics by using the color filter.

In addition, it is not necessary to thicken the green pixels of the color filter, and to achieve high luminance or high contrast in the green color region of the high color density, it is desired to have a blue color. And the green pigment dispersion with high brightness, but it does not exist.

The present invention has been made in view of the above circumstances, and a second object is to provide a green color material dispersion liquid which exhibits greenish blue color, excellent color material dispersion stability, and high luminance; and the color material dispersion liquid and solvent resolubility are superior and high. a photosensitive colored resin composition for color filters which is excellent in color reproducibility and which is excellent in color reproducibility; a color filter having a high luminance and a high contrast and excellent color reproducibility for a photosensitive colored resin composition for a color filter; and a liquid crystal display device having high luminance and excellent color reproducibility by using the color filter and Organic light emitting display device.

The color material dispersion liquid for color filters of the present invention for solving the first object of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent; and the dispersant is as follows At least one of the block copolymer (P1) and the following salt block copolymer (P2); P1: having an A block comprising the structural unit represented by the following general formula (I) and containing a carboxyl group-containing single a block copolymer of a B block of a bulk constituent unit; P2: at least a part of a nitrogen portion at a terminal end of the constituent unit represented by the above general formula (I) of the block copolymer, and a general formula selected from the group consisting of a salt type block copolymer formed by forming a salt of one or more compounds of the group consisting of the compounds represented by (1) to (3); the acid value of the dispersant is from 1 to 18 mgKOH/g, and the glass transition temperature of the dispersant Above 30 ° C; [Chemical 1]

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bond group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ³ Further, it may be bonded to each other to form a ring structure; in the general formula (1), R ^a represents ^a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or Benzyl, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a carbon number of 1 a (meth)acryloyl group of an alkyl group of ~4; in the general formula (2), R ^b , R ^{b '} and R ^b" each independently represent a hydrogen atom, an acidic group or an ester group thereof, and may have a substituent. a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -OR ^f , and R ^f 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 carbon number of 1 ~4 alkyl-linked (meth) acryloyl group, X represents chlorine , A bromine atom, or iodine atom; general formula (3), R ^c and R ^d each independently represent a hydrogen atom, a hydroxyl group, a straight-chain carbon number of 1 to 20, the branched-chain or cyclic alkyl group, a vinyl group And a phenyl group or a benzyl group having a substituent, or -OR ^e , and R ^e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, and a benzene group which may have a substituent. a (meth)acrylinyl group bonded to a benzyl group or a alkyl group having 1 to 4 carbon atoms; wherein at least one of R ^c and R ^d contains a carbon atom.

The color material dispersion liquid for color filters of the present invention for solving the second object of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent; wherein the color material system contains CI Pigment green 59; the above dispersant is a polymer having the following structural unit represented by the general formula (I);

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bond group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ³ They can also be bonded to each other to form a ring structure.)

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

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

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

Further, the present invention provides an organic light-emitting display device comprising the above-described color filter of the present invention and an organic light-emitting body.

According to the first aspect of the invention, it is possible to provide a color material dispersion liquid which is excellent in dispersion stability of a color material and which can produce a photosensitive colored resin composition excellent in development adhesiveness and solvent resolubility while suppressing development residue; A photosensitive colored resin composition for a color filter which is excellent in stability, suppresses development residue, develops adhesiveness and solvent resolubility, and can form a comparatively superior coloring layer; and uses the color filter for sensitization A color filter formed of a coloring resin composition; 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, it is possible to provide a green color material dispersion liquid which exhibits greenish blue color, excellent dispersion stability of color materials, and high luminance; and the color material dispersion liquid and solvent are excellent in resolubility and can be high A photosensitive coloring resin composition for a color filter of a color layer excellent in color reproducibility and a high contrast, and a high-intensity and high contrast and excellent color reproducibility of a photosensitive colored resin composition using the color filter 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.

1‧‧‧Transparent substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧ opposite substrate

30‧‧‧Liquid 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‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

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

Fig. 2 is a schematic view showing an example of a liquid crystal display device of the present invention.

Fig. 3 is a schematic view showing an example of an organic light emitting display device of the present invention.

I. The first invention

Hereinafter, the color material dispersion liquid for color filters, the photosensitive coloring resin composition for color filters, the color filter, the liquid crystal display device, and the organic light-emitting display device of the present invention will be described in order.

Still, in the present invention, the light includes electromagnetic waves of wavelengths of visible and non-visible regions, and further includes radiation, and the radiation system includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

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

In the present specification, unless otherwise specified, the chromaticity coordinates x and y are those in the XYZ color system of JIS Z8701 which is measured by the C light source.

I-1. The first color material dispersion related to the present invention

The first color material dispersion liquid for a color filter according to the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent; and the dispersant is the following block copolymer (P1) And at least one of the following salt type block copolymers (P2); P1: having an A block comprising a structural unit represented by the following general formula (I) and a B-inclusion comprising a constituent unit derived from the carboxyl group-containing monomer a block copolymer of a segment; P2: at least a part of a nitrogen moiety at a terminal of the structural unit represented by the above general formula (I) in the block copolymer, and a general formula (1) to (3) selected from Compound shown A salt type block copolymer of a salt formed by one or more compounds of the group of substances; the acid value of the dispersant is 1 to 18 mgKOH/g, and the glass transition temperature of the dispersant is 30 °C or higher.

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bond group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ³ Further, it may be bonded to each other to form a ring structure; in the general formula (1), R ^a represents ^a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or Benzyl, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a carbon number of 1 (4) an alkylene-bonded (meth) acrylonitrile group; in the general formula (2), R ^b , R ^{b '} and R ^b" each independently represent a hydrogen atom, an acidic group or an ester group thereof, and may have a substitution. a straight chain, a branched chain or a cyclic alkyl group having a carbon number of 1 to 20, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -OR ^f , R ^f Further, it may have a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms of a substituent, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or a carbon number. 1~4 alkyl-linked (methyl) acrylonitrile group, X table A chlorine atom, a bromine atom, or iodine atom; (3), R ^c and R ^d each independently represent a hydrogen atom in general formula, a hydroxyl group, a straight-chain carbon atoms of 1 to 20, the branched-chain or cyclic alkyl group, vinyl a phenyl group or a benzyl group which may have a substituent, or -OR ^e , and R ^e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. a phenyl group or a benzyl group or a (meth) acryl fluorenyl group bonded via a C 1-4 alkyl group; wherein at least one of R ^c and R ^d contains a carbon atom.

The color material dispersion of the present invention is formed by using a salt copolymer having a specific acid value and a specific glass transition temperature, a block copolymer (P1) containing the above specific constituent unit, and a salt formed by the block copolymer and the specific compound. Since at least one of the segment copolymers (P2) is used as a dispersing agent, it is possible to produce a photosensitive colored resin composition which is excellent in dispersion stability of a color material and which is excellent in development adhesiveness and solvent resolubility while suppressing development residue. Further, the photosensitive coloring resin composition for a color filter prepared by using the color material dispersion liquid can form a comparatively superior color layer.

By using a block copolymer (P1) having the above specific constituent unit having the above-mentioned specific acid value and a specific glass transition temperature, and a salt-type block copolymer (P2) in which the block copolymer forms a salt with the above specific compound (P2) At least one of the above-mentioned effects as a dispersing agent is not explained, but it can be estimated as follows.

It has been known in the past as a pigment dispersant to enhance dispersibility by having a block copolymer comprising an A block having a specific repeating unit having an amine group or an ammonium salt group and a B block having a repeating unit having an acidic group. Or dispersion stability and alkali developability (for example, Patent Documents 1, 2 and 4).

However, as a result of the study by the inventors of the present invention, the results described in Patent Document 1 have in particular that the development adhesiveness has not reached a practical level. According to the method described in Patent Document 1, the reason for the reason is that the block copolymer is contained in the carboxylic acid as shown in the comparative example described later. The portion of the ester derived from the alcohol has a specific repeating unit of the alkylene oxide chain, so the glass transition temperature becomes low. When the glass transition temperature of the block copolymer as the pigment dispersant is a temperature lower than the temperature of the developer or a temperature close to the temperature of the developer, the molecular motion of the dispersant increases during development, and as a result, the development adhesiveness is lowered.

Further, in the methods described in Patent Documents 2 and 4, in particular, the development adhesiveness is not at a practical level. In the methods described in Patent Documents 2 and 4, as shown in the comparative example described later, the reason is that the acid value of the dispersing agent is higher than the value specified in the present case. Therefore, although the developability is excellent, the polarity is too high and the peeling is likely to occur. . In the methods described in Patent Documents 2 and 4, it is presumed that the development adhesiveness is not at a practical level because there is no concept that the dispersant satisfies both the specific low acid value and the specific high glass transition temperature.

As a result of intensive studies, the present inventors have found that if the acid value of the specific block copolymer or the salt block copolymer is high, the development adhesiveness cannot reach a practical level, and the solvent resolubility deteriorates; When the value is a low acid value of a specific value or less, the effect of suppressing the development residue is obtained, and good development adhesiveness which is less likely to cause peeling can be obtained, and the solvent resolubility is excellent. On the other hand, it has been found that even if the specific block copolymer or the salt block copolymer is a low acid value of the above specific value or less, if the glass transition temperature is lower than a predetermined value, the development adhesiveness does not reach a practical level; However, when a block copolymer or a salt block copolymer having a glass transition temperature higher than the developer temperature by 30 ° C or higher is used, the development adhesiveness is excellent. When a block copolymer or a salt block copolymer having a glass transition temperature of 30 ° C or more higher than the temperature of the developer is used, it is estimated that the molecular movement of the dispersant during development is suppressed, so that the deterioration of the development adhesiveness is suppressed.

The color material dispersion liquid according to the present invention may contain 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.

Hereinafter, each component of the color material dispersion liquid according to the present invention will be described in order from the characteristic dispersing agent of the present invention.

<dispersant>

In the present invention, at least one of the block copolymer (P1) and the salt block copolymer (P2) is used as a dispersant, and the acid value of the dispersant is from 1 to 18 mgKOH/g. The glass transition temperature of the agent is 30 ° C or higher.

The structural unit represented by the above general formula (I) contained in the A block has a salt-based property and has a function as a site for adsorbing a color material. Further, when at least a part of the nitrogen portion of the terminal group represented by the general formula (I) and a compound selected from the group consisting of the above-described general formulas (1) to (3) form a salt, The salt forming portion has a function 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 has a function as a solvophilic block. Therefore, the block copolymerization system of the present invention functions as a color material dispersant by the A block which adsorbs with the color material and the B block sharing function which has solvent affinity.

[block copolymer] {A block} (constitutive unit shown in general formula (I))

In the general formula (I), A is a direct bond or a divalent bond group. By direct bonding, it is meant 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 other atoms.

The divalent bond group in A may, for example, be an alkylene group having 1 to 10 carbon atoms. An aryl 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 alkyl group) and combinations thereof .

Among them, from the viewpoint of dispersibility, A in the general formula (I) is preferably a direct bond, a -CONH- group, or a divalent bond group containing a -COO- group.

R ² and R ³ may further contain a hydrocarbon group in a hydrocarbon group of a hetero atom, and examples thereof include an alkyl group, an aralkyl group, and an aryl group.

The alkyl group may, for example, be 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 or a cyclohexyl group, and the alkyl group preferably has a carbon number. It is 1 to 18, and more preferably it is a methyl group or an ethyl group.

The aralkyl group may, for example, be a benzyl group, a phenethyl group, a naphthylmethyl group or a biphenylmethyl group. The number of carbon atoms of the aralkyl group is preferably from 7 to 20, more preferably from 7 to 14.

Further, 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 from 6 to 24, more preferably from 6 to 12. Further, the above preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

The hydrocarbon group containing a hetero atom is a structure in which the hydrocarbon group has a carbon atom substituted by a hetero atom. Examples of the hetero atom which may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a ruthenium atom.

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

The relationship between R ² and R ³ to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. The ring structure formed by R ² and R ³ may also contain a hetero atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring and a piperidine ring. A porphyrin ring or the like.

In the present invention, R ² and R ³ are each independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a pyrrolidine ring or a piperidine ring formed by bonding R ² and R ³ , A porphyrin ring.

The constituent unit represented by the above general formula (I) may, for example, be dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate or diethylamine (meth)acrylate. a (meth) acrylate containing an alkyl-substituted amine group, such as a ethyl ester or diethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethyl A (meth)acrylamide or the like containing an alkyl-substituted amine group such as a propylaminopropyl (meth) acrylamide. Among them, from the viewpoint of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylamino group are preferably used. Propyl (meth) acrylamide.

The constituent unit represented by the general formula (I) may be composed of one type or two or more constituent units.

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

In the range which achieves the object of the present invention, the A block may have a constituent unit other than the constituent unit represented by the general formula (I), and may be a constituent unit which can be copolymerized with the constituent unit represented by the general formula (I). contain. For example, as a constituent unit other than the constituent unit represented by the general formula (I), which may be contained in the salt-based block portion, the "other constituent unit" listed in the B block described later may be used, and specific examples thereof include a general formula described later. The constituent unit shown in (II).

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

Further, in the block copolymer before salt formation, the content ratio of the constituent unit represented by the general formula (I) is based on the total constituent unit of the block copolymer, from the viewpoint of good dispersibility and dispersion stability. The total mass is preferably from 5 to 60% by mass, more preferably from 10 to 50% by mass. Moreover, the content ratio of each constituent unit in the above-mentioned block copolymer is calculated from the packing quality in the case of the block copolymer before the formation of the synthetic salt.

In addition, the constituent unit represented by the general formula (I) may have an affinity with the color material, and may be composed of one type or two or more constituent units.

{B block}

The B block system does not contain the structural unit represented by the above general formula (I), but contains a block derived from a constituent unit of the carboxyl group-containing monomer. The B block is preferably a monomer which is copolymerized with a monomer which can be derived from a structural unit represented by the general formula (I) and which has an unsaturated double bond, and is appropriately selected by mixing a solvent in a solvent-friendly manner. use. As a standard, it is preferable to introduce a B block so that the solubility of the copolymer at 23 ° C is 20 (g / 100 g solvent) or more with respect to the solvent to be used in combination.

(from the constituent unit of the carboxyl group-containing monomer)

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

Examples of such a monomer include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, isaconic acid, crotonic acid, and the like. Gui Skin acid, acrylic acid dimer, and the like. Further, an addition reaction of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate with a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride may be used. -carboxy-polycaprolactone mono(meth)acrylate or the like. Further, as the carboxyl group precursor, an acid anhydride group-containing monomer such as maleic anhydride, isaconic anhydride or citraconic anhydride may be used. Among them, (meth)acrylic acid is particularly preferred 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 in such a manner that the acid value of the block copolymer is within the range of the specific acid value, and there is no particular The total mass of the total constituent units of the block copolymer is preferably from 0.05 to 4.5% by mass, more preferably from 0.07 to 3.7% by mass.

When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue is excellent, and if it is at most the above upper limit value, deterioration of development adhesiveness or solvent redissolution can be prevented. Sexual deterioration.

In addition, the constituent unit derived from the carboxyl group-containing monomer may be one of the above-mentioned specific acid valences, and may be composed of one type or two or more constituent units.

(other constituent units)

In the B block, from the viewpoint of improving the solvophilic property, in addition to the constituent unit derived from the carboxyl group-containing monomer, a constituent unit for enhancing the solvophilic property may be further contained.

The constituent unit constituting the B block may, for example, be a monomer having an unsaturated double bond which is copolymerizable with a monomer derived from a structural unit represented by the general formula (I), and is preferably a general formula (II). Show the constituent units.

(In general formula (II), A' is a direct bond or a divalent bond group, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrocarbon group, -[CH(R ⁶ )-CH(R ⁷ )-O ] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ represents a monovalent group. R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, a hydrocarbon group, -CHO And a monovalent group represented by -CH ₂ CHO or -CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The above hydrocarbon group may have a substituent.

x is an integer from 1 to 18, y is an integer from 1 to 5, and z is an integer from 1 to 18. )

In the general formula (II), A' can be set to be the same as A in the general formula (I). Among them, from the viewpoint of solubility in an organic solvent, a direct bond, a -CONH- group or a divalent bond group containing a -COO- group is preferred.

In the general formula (II), R ⁵ represents a hydrocarbon group, -[CH(R ⁶ )-CH(R ⁷ )-O] _x -R ⁸ or -[(CH ₂ ) _y -O] _z -R ⁸ .

The hydrocarbon group in R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group or an aryl group.

The alkyl group having 1 to 18 carbon atoms may be any of a straight chain, a branched chain, and a cyclic ring, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, and a 2-ethyl group. Hexyl group, 2-ethoxyethyl, cyclopentyl, cyclohexyl, Basis A group, a dicyclopentyl group, a dicyclopentenyl group, an adamantyl group, a lower alkyl group-substituted adamantyl group or the like.

The above alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. One. Examples of such an alkenyl group include a vinyl group, an allyl group, and an allyl group. The position of the double bond of the alkenyl group is not limited, and from the viewpoint of the reactivity of the obtained polymer, it is preferred to have a double bond at the terminal of the alkenyl group.

Examples of the substituent of the aliphatic hydrocarbon group such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

The aryl group may, for example, be a phenyl group, a biphenyl group, a naphthyl group, a tolyl group or a xylyl group, and may further have a substituent. The number of carbon atoms of the aryl group is preferably from 6 to 24, more preferably from 6 to 12.

Further, 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 from 7 to 20, more preferably from 7 to 14.

The substituent of the aromatic ring such as an aryl group or an aralkyl group may, for example, be an alkyl group, a nitro group or a halogen atom, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

Further, the above preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

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

The hydrocarbon group in the above R ⁸ may be the same as those shown in the above R ⁵ .

R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be any of a linear chain, a branched chain, or a cyclic group.

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

In the above-mentioned R ⁵ , it is preferred to select a solvent which is superior to the solvent to be described later. Specifically, for example, a glycol ether generally used as a solvent for a colored resin composition for a color filter is used as the solvent. In the case of a solvent such as an acetate system, an ether system or an ester system, a methyl group, an ethyl group, an isobutyl group, a n-butyl group, a 2-ethylhexyl group or a benzyl group is preferable.

Further, the above R ⁵ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group or an isocyanate, or may be substituted as described above insofar as it does not inhibit the dispersion property of the block copolymer or the like. After the synthesis of the block copolymer, it is reacted with a compound having the above substituent to form the above substituent.

The number of constituent units constituting the B block is not particularly limited, but is preferably from 10 to 300, more preferably 10 from the viewpoint of effectively acting on the solvophilic portion and the coloring material portion and enhancing the dispersibility of the color material. ~100, and even better 10~70.

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

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

The B block may be appropriately selected from the constituent units in such a manner as to function as a solvophilic moiety, and the constituent unit represented by the above formula (II) may be composed of one type or two or more constituent units. Two or more constituent units contained in the B block may be randomly arranged 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 the development adhesiveness. In the case where the constituent unit derived from the hydroxyl group-containing monomer is contained, it is considered to be easy to interact with glass or metal which is usually used as a substrate, and it is considered that the development adhesiveness can be improved. In the case of the B block, when the constituent unit derived from the hydroxyl group-containing monomer is contained, the development speed is further improved.

Further, the hydroxyl group herein refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As a constituent unit derived from the hydroxyl group-containing monomer, a monomer having an unsaturated double bond and a hydroxyl group which can be copolymerized with a monomer derived from a structural unit represented by the general formula (I) can be used. Examples of such a monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxy(meth)acrylate. Butyl ester, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate ε-caprolactone 1 molar addition, (methyl ) 2-hydroxy-3-phenoxypropyl acrylate or the like.

From the viewpoint of improving developability, those having a hydroxyl group of a first order are preferred as those having a hydroxyl group of a second order. Further, the first-order hydroxyl group means a hydroxyl group in which a carbon atom bonded to a hydroxyl group is a first-order carbon atom, and the second-order hydroxyl group means a hydroxyl group in which a carbon atom to which a hydroxyl group is bonded is a secondary carbon atom.

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 the development adhesiveness, it is preferred to use a glass transition temperature of a homopolymer of each monomer. The value (Tgi) is a hydroxyl group-containing monomer of 0 ° C or more, and more preferably a hydroxyl group-containing monomer of 10 ° C or more.

From the viewpoint of improving the development adhesiveness, among them, it is preferably selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate. More than one species.

In addition, in the block copolymer (P1) before salt formation, the content ratio of the constituent unit derived from the hydroxyl group-containing monomer is preferably 1% by mass or more based on the total mass of the total constituent units of the block copolymer. More preferably, it is 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 4% by mass or more. If it is more than the above lower limit value, it can be made into a development adhesiveness. 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. If it is less than or equal to the above upper limit, it can be made preferable from the viewpoint of improving the introduction ratio of other useful monomers. Further, the content ratio of the above constituent units is calculated from the packing quality at the time of synthesis of the block copolymer before salt formation.

Further, in the present invention, the B block preferably contains a constituent unit derived from an aromatic group-containing monomer from the viewpoint of enhancing solvent resolubility. In the case where the constituent unit derived from the aromatic group-containing monomer is contained, it is considered that the solvent resolubility can be improved because the compatibility with the solvent or other components is easily improved.

As a constituent unit derived from the aromatic group-containing monomer, a monomer having an unsaturated double bond and an aromatic group which can be copolymerized with a monomer derived from a structural unit represented by the general formula (I) can be used. Examples of such a monomer include acrylates such as benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and phenoxyethyl (meth)acrylate. A styrene such as styrene or a vinyl ether such as phenyl vinyl ether.

As will be described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving the development adhesiveness, it is preferred to use a glass transition temperature of a homopolymer of each monomer. The value (Tgi) is an aromatic group-containing monomer of 0 ° C or more, and more preferably an aromatic group-containing monomer of 10 ° C or more.

From the viewpoint of easily improving resolubility, among them, it is preferably selected from the group consisting of benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and (meth)acrylic acid. One or more selected from the group consisting of phenoxyethyl esters, more preferably one or more selected from the group consisting of benzyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate .

Further, in the block copolymer (P1) before salt formation, the content ratio of the constituent unit derived from the aromatic group-containing monomer is based on the total constituent unit of the block copolymer from the viewpoint of enhancing solvent resolubility. The total mass 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. If it is more than the above lower limit value, it can be made into a solvent resolubility. 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. If it is less than or equal to the above upper limit, it can be made preferable from the viewpoint of improving the introduction ratio of other useful monomers.

Further, among them, the B-block having a solvophilic property preferably contains (i) a constituent unit derived from a hydroxyl group-containing monomer and an aromatic group-containing group from the viewpoint of improving development adhesiveness and solvent resolubility. And a component of the monomer; and (ii) at least one of constituent units derived from the carboxyl group-containing and aromatic group-containing monomer.

In the case where (i) the constituent unit derived from the hydroxyl group-containing monomer and the constituent unit derived from the aromatic group-containing monomer are contained, respectively, it is preferably contained in an amount of 1 part by mass based on the constituent unit derived from the aromatic group-containing monomer. The constituent unit of the hydroxy monomer is 0.15 parts by mass or more, more preferably 0.5 parts by mass or more. When it is more than the above lower limit value, it is excellent in development adhesiveness. In the same manner, the amount of the constituent unit derived from the hydroxyl group-containing monomer is preferably 15 parts by mass or less, more preferably 7 parts by mass or less, based on 1 part by mass of the constituent unit derived from the aromatic group-containing monomer. When it is at most the above upper limit value, it can be made into a solvent resolubility superior. In particular, the value (Tgi) of the glass transition temperature of the homopolymer is 1 part by mass or more of the constituent unit derived from the aromatic group-containing monomer at 10 ° C or higher, and the glass transition temperature of the homopolymer is contained in the above range. The value (Tgi) becomes 10 A constituent unit derived from a hydroxyl group-containing monomer above °C. By containing each component in accordance with the above lower limit value, it is possible to obtain a development adhesiveness superiority, and by containing each component in accordance with the above upper limit value, it is possible to obtain a solvent solubility superiority.

Further, (ii) a monomer having a hydroxyl group and an aromatic group in a constituent unit derived from a hydroxyl group-containing and aromatic group-containing monomer, for example, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2 - propylene methoxyethyl 2-hydroxyethyl-decanoic acid or the like. 2-hydroxy-3-phenoxypropyl (meth)acrylate is a glass transition temperature (Tgi) of a homopolymer of 10 ° C or more, and an effect obtained from a constituent unit derived from a hydroxyl group-containing monomer can be obtained. From the viewpoint of any of the effects obtained from the constituent unit of the aromatic group-containing monomer, it is preferably used. That is, it is preferable from the viewpoint of improving the development adhesiveness, the development speed, and the solvent resolubility.

(ii) In the case where the constituent unit derived from the hydroxyl group-containing and aromatic group-containing monomer is contained, since the development adhesiveness, the development speed, and the solvent resolubility can be improved by one constituent unit, the other functions can be improved. The advantage of the introduction ratio of the monomer.

Further, as described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving the development adhesiveness, it is preferred to use a glass transition temperature of a monomer homopolymer. The monomer having a value (Tgi) of 10 ° C or more is 75% by mass or more, and more preferably 85% by mass or more in the total amount of the B block.

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

Further, the amine valence of the block copolymer (P1) before salt formation is not particularly limited, and from the viewpoint of dispersibility of color material and dispersion stability, the lower limit is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 60 mgKOH/g or more. Further, the upper limit is preferably 140 mgKOH/g or less, more preferably 130 mgKOH/g or less, still more preferably 120 mgKOH/g or less. When it is more than the above lower limit value, the dispersion stability is further superior. In addition, when it is at most the above upper limit value, compatibility with other components is excellent, and solvent resolubility is improved.

Further, in the present invention, the amine valence of the block copolymer before salt formation is the amount of hydrochloric acid required for 1 g of the solid component of the block copolymer before neutralization of the salt to form an equivalent amount of hydr The mass (mg) of potassium is a value measured by the method described in JIS K 7237.

The weight average molecular weight Mw of the block copolymer is not particularly limited, and is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, still more preferably from 3,000 to 12,000, from the viewpoint of improving dispersibility and dispersion stability of the color material. .

Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) and is a standard polystyrene equivalent value.

Further, in the present invention, the weight average molecular weight Mw of the block copolymer is determined by GPC (gel permeation chromatography) to be a standard polystyrene equivalent value. For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, and the eluting solvent was N-methylpyrrolidone to which 0.01 mol/liter lithium bromide was added, and the calibration curve was set to Mw377400 by polystyrene standard. 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above is Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (made by Tosoh Co., Ltd.), and the measuring column is set to TSK-GEL Conducted by ALPHA-MX2 (Tosoh Corporation). Moreover, the macromonomer, the salt type block copolymer, and the graft copolymer which are the raw materials of the block copolymer are carried out under the above conditions.

In the present invention, the arrangement of the respective 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, from the viewpoint of superior dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

The method for producing the block copolymer is not particularly limited, and a block copolymer can be produced by a known method. Among them, it is preferably produced by a living polymerization method. This is due to the fact that chain migration or deactivation is less likely to occur, a copolymer having a molecular weight can be produced, and dispersibility can be improved. The living polymerization method may, for example, be a living anionic polymerization method such as a living radical polymerization method or a base transfer polymerization method, or a living cationic polymerization method. By sequentially polymerizing the monomers by such methods, a copolymer can be produced. For example, the A block is first produced, and the A block is polymerized with the constituent unit constituting the B block to produce a block copolymer. Further, in the above production method, the polymerization order of the A block and the B block may be reversed. Further, the A block and the B block may be separately produced, and then the A block and the B block may be coupled.

[salt block copolymer]

In the present invention, at least a part of the nitrogen moiety at the terminal of the structural unit represented by the above general formula (I) and the compound selected from the above general formulas (1) to (3) may be used. A salt type block copolymer of a salt formed by one or more compounds of the group.

In the above-mentioned salt-type block copolymer, the salt-forming portion in the structural unit represented by the above general formula (I) is preferably used from the viewpoint of further improving the color material adsorption property and improving the dispersibility of the color material.

(a compound selected from the group consisting of the compounds represented by the above general formulas (1) to (3))

In the above general formulas (1) to (3), as ^a linear chain of 1 to 20 carbon atoms in R ^a , R ^b , R ^{b '} , R ^b" , R ^c , R ^d , R ^e and R ^f The branched or cyclic alkyl group may be either a straight chain or a branched chain, or may have a cyclic structure, and specifically, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, or a n-butyl group. Base, isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, dodecyl, a cyclopentyl group, a cyclohexyl group, a tetradecyl group, an octadecyl group, etc., preferably, for example, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, more preferably, for example, a carbon number of 1 a linear, branched or cyclic alkyl group of ~8.

Further, among R ^a , R ^c , R ^d and R ^e , the substituent of the phenyl group or the benzyl group which may have a substituent may, for example, be an alkyl group having 1 to 5 carbon atoms, a fluorenyl group or a fluorene group. Base.

In R ^b , R ^{b '} , R ^b" and R ^f , examples of the substituent of the phenyl group or the benzyl group which may have a substituent include an acidic group or an ester group thereof, and an alkyl group having 1 to 5 carbon atoms. , sulfhydryl, decyloxy and the like.

Further, R ^b , R ^{b '} , R ^{b "} and R ^f may be a linear, branched or cyclic alkyl group or a vinyl substituent having 1 to 20 carbon atoms which may have a substituent. For example, an acidic group or an ester group thereof, a phenyl group, a decyl group, a decyloxy group or the like can be mentioned.

In the case of R ^b , R ^{b '} , R ^{b "} and R ^f , the acidic group means a group which exhibits acidity when a proton is released in water. Specific examples of the acidic group include a carboxyl group (-COOH) and a sulfonic acid. (-SO ₃ H), phosphinyl (-P(=O)(OH) ₂ ), phosphonic acid subunit (>P(=O)(OH)), boric acid (-B(OH) ₂ ) The phosphinic acid group (>BOH) may be an anion in which a hydrogen atom has been dissociated, such as a carboxy group (-COO ^- ), and may also be an acidic salt which forms a salt with an alkali metal ion such as a sodium ion or a potassium ion. .

Further, examples of the ester group of the acidic group include a carboxylate (-COOR), a phosphate (-SO ₃ R), a phosphate (-P(=O)(OR) ₂ ), and a phosphonic acid subunit (> P(=O)(OR)), borate ester (-B(OR) ₂ ), hypoborate (>BOR), and the like. Among them, the ester group as the acidic group is preferably a carboxylate (-COOR) from the viewpoint of dispersibility and dispersion stability. Further, R is a hydrocarbon group, and is not particularly limited. From the viewpoint of dispersibility and dispersion stability, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

The compound of the above general formula (2) preferably has an anion selected from the group consisting of a carboxyl group, a boric acid group, a borous acid group, and the like, from the viewpoints of dispersibility, dispersion stability, alkali developability, and development residue suppression. And one or more functional groups of the alkali metal salt or the like, and more preferably a functional group selected from the group consisting of a carboxyl group, a carboxy group, a carboxylate group, and a carboxylic acid ester.

In the case where the compound of the above formula (2) has an acidic group and an ester group thereof (hereinafter referred to as an acidic group or the like), the acidic group or the like and the halogen atom side hydrocarbon of the compound may be bonded to the terminal. When a salt is formed in the nitrogen portion, and a salt is formed in the nitrogen portion of the terminal portion and the acidic group, it is estimated that the nitrogen portion at the terminal end and the halogen atom side hydrocarbon can stably form a salt. Further, it is presumed that the dispersibility and the dispersion stability can be improved by adsorbing the color material by the salt forming portion which is stably present.

In the case where the compound of the above formula (2) has the above acidic group or the like, it may have two or more of the above acidic groups. In the case of having two or more of the above acidic groups, the plurality of acidic groups and the like may be the same or different. The number of the acidic groups and the like of the compound of the above formula (2) is preferably from 1 to 3, more preferably from 1 to 2, still more preferably one.

At least one of R ^a in the general formula (1), R ^b , R ^{b '} and R ^b′ in the general formula (2), and at least one of R ^c and R ^{d in} the general formula (3) In the case of the aromatic ring, the affinity with the skeleton of the color material described later can be improved, and the dispersibility and dispersion stability of the color material are excellent, and a comparatively excellent coloring composition can be obtained, which is preferable.

The molecular weight of one or more compounds selected from the group consisting of the above general formulas (1) to (3) is preferably 1000 or less, more preferably 50 to 800, and even more preferably 50 from the viewpoint of improving the dispersibility of the color material. ~400, better 80~350, best 100~330.

Examples of the compound represented by the above general formula (1) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, and mono-n-propylsulfuric acid. Further, a hydrate such as p-toluenesulfonic acid monohydrate can also be used. The compound represented by the above formula (2) may, for example, be a methyl chloride group, a methyl bromide group, an ethyl chloride group, an ethyl bromide group, a methyl iodide group, an ethyl iodide group or a n-butyl chloride group. Hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, cetyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide , chlorobenzene, α-chlorophenyl acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-iodophenylbenzoic acid, Chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3-(bromomethyl)phenylboronic acid, and the like. Examples of the compound represented by the above formula (3) include monobutylphosphoric acid, dibutylphosphoric acid, methylphosphoric acid, dibenzylphosphoric acid, diphenylphosphoric acid, phenylphosphinic acid, phenylphosphoric acid, and dimethyl. Alkyl acryloxyethyl acid phosphate or the like.

From the viewpoint of particularly superior dispersion stability, it is preferably selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethyl propylene methoxyethyl acid phosphate, dibutyl phosphoric acid, benzyl chloride, and bromine. One or more selected from the group consisting of a benzyl group, a vinyl sulfonic acid, and a p-toluenesulfonic acid monohydrate, and among them, a phenylphosphinic acid, a phenylphosphonic acid, a benzyl bromide, and One or more of the group consisting of p-toluenesulfonic acid monohydrate.

Moreover, it is also suitable for use from the viewpoint of improving the suppression effect of the development residue by combining with the block copolymer (P1) having an acid value, which is excellent in dispersion stability. a compound of the formula (2) wherein the base group and the ester group thereof are also suitably selected from the group consisting of α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, and 4-chloromethylbenzoic acid. One or more groups of 4-bromomethylbenzoic acid and 4-iodophenylbenzoic acid.

In the salt-type block copolymer, the content of one or more compounds selected from the group consisting of the above general formulas (1) to (3) is due to the nitrogen portion at the end of the constituent unit represented by the general formula (I). Since the salt is formed in the nitrogen portion of the terminal of the general formula (I), one or more compounds selected from the group consisting of the above general formulas (1) to (3) are used. 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.2 mol or more, and particularly preferably 0.3 mol or more. When it is at least the above lower limit value, it is easy to obtain an effect of improving the dispersibility of the color material due to salt formation. Similarly, it is preferably 1 mol 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 it is at most the above upper limit value, it is preferable to have a development adhesiveness or a solvent resolubility.

In addition, one or more compounds selected from the group consisting of the above-mentioned general formulas (1) to (3) may be used alone or in combination of two or more. When two or more types are combined, the total content thereof is preferably within the above range.

In the method of preparing the salt-type block copolymer, for example, one or more compounds selected from the group consisting of the above general formulas (1) to (3) are added to the solvent in which the block copolymer is dissolved or dispersed. The mixture is stirred and heated as needed.

In the block copolymer, the nitrogen moiety at the terminal of the structural unit represented by the general formula (I) and the one or more compounds selected from the group consisting of the general formulas (1) to (3) are formed into a salt. The case and the ratio thereof can be confirmed by a known method such as NMR.

The amine valence of the obtained salt type block copolymer (P2) is only before salt formation The value of the amount of the salt formed by the block copolymer (P1) is small. However, since the salt-forming portion has the same or more enhanced color material adsorption site as the nitrogen portion at the end corresponding to the amine group, there is a tendency to enhance the dispersibility of the color material or the dispersion stability of the color material by salt formation. Further, the salt formation site is similar to the amine group, and if it is too large, it adversely affects the solvent resolubility. Therefore, in the present invention, the amine valence of the block copolymer (P1) before salt formation can be used as an index for improving the dispersion stability of the color material and the solvent resolubility. The amine value of the obtained salt type block copolymer (P2) is preferably 0 to 130 mgKOH/g, more preferably 0 to 120 mgKOH/g.

When it is at most the above upper limit value, the compatibility with other components is excellent, and the solvent resolubility is good.

Further, in the salt-type block copolymer (P2), the amine valence of the salt-type block copolymer of the salt formed by the compound of the above formula (2) can be determined by the method described in JIS K 7237. value. In the compound of the above formula (2), since the nitrogen moiety at the terminal of the structural unit represented by the general formula (I) forms a salt with the halogen atom side hydrocarbon, the salt formation is not changed even by the measurement method. State, so the amine price can be determined.

On the other hand, in the salt type block copolymer (P2), the amine valence of the salt type block copolymer formed by the compound represented by the above general formula (1) or (3) is formed by the above salt. The amine valence of the block copolymer was calculated as follows. In the compound of the above formula (1) or (3), since the nitrogen moiety at the terminal of the structural unit represented by the general formula (I) forms a salt with an acidic group, it is determined by the method described in JIS K 7237. The amine valence of such a salt type block copolymer causes a change in the state of salt formation, and the correct value cannot be measured.

First, the amine of the block copolymer (P1) before salt formation is obtained by the above method. price. Next, the 13 C-NMR spectrum of the salt type block copolymer was measured by a nuclear magnetic resonance apparatus, and the obtained nitrogen spectrum of the terminal part of the structural unit represented by the above general formula (I) was obtained by The ratio of the peak of the carbon atom adjacent to the nitrogen atom and the integrated value of the peak of the carbon atom adjacent to the nitrogen atom forming the salt, and the constituent unit of the salt type block copolymer relative to the general formula (I) The nitrogen moiety at the terminal end is selected from the reaction rate (the ratio of the nitrogen sites forming the end of the salt) of one or more compounds selected from the group consisting of the above general formula (1) or (3). The nitrogen moiety at the end of the constituent unit represented by the general formula (I) in which the salt of the compound of the above formula (1) or (3) is formed is selected to have an amine price of 0. The amine content of the front block copolymer (P1) formed by the salt measured by the method described in JIS K 7237 × (the nitrogen content ratio (%) of the terminal of the formed salt calculated from the 13C-NMR spectrum / 100 It is calculated by subtracting the amine valence consumed by salt formation from the amine valence of the block copolymer before salt formation.

The amine valence of the salt-type block copolymer (P2) = {the amine valence of the salt-forming front block copolymer (P1) by the method described in JIS K 7237} - {Measured by the method described in JIS K 7237 The salt form the amine valence of the anterior block copolymer (P1)}×{the ratio of the nitrogen sites at the end of the formed salt calculated from the 13C-NMR spectrum (%)/100}

The acid value of the dispersing agent used in the present invention is a lower limit of 1 mgKOH/g or more from the viewpoint of the effect of suppressing the development residue. Among them, the acid value of the dispersing agent is more preferably 2 mgKOH/g or more from the viewpoint of further suppressing the effect of the development residue. Moreover, the acid value of the dispersing agent used in the present invention has an upper limit of 18 mgKOH/g or less from the viewpoint of preventing deterioration of development adhesiveness or deterioration of solvent resolubility. In particular, the acid value of the dispersing agent is preferably 16 mgKOH/g or less, and more preferably 14 mgKOH/g or less from the viewpoints of good development adhesiveness and solvent resolubility.

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

As described above, the acid value of the block copolymer (P1) before salt formation is the mass (mg) of potassium hydroxide required for neutralizing the acidic component contained in 1 g of the solid content of the block copolymer. The value measured by the method described in JIS K 0070 is shown.

Further, the acid value of the salt-type block copolymer (P2) of the salt-type block copolymer which forms a salt by the compound represented by the above general formula (2) is also a value measured by the method described in JIS K 0070. . In the compound of the above formula (2), since the nitrogen moiety at the terminal of the structural unit represented by the general formula (I) forms a salt with the halogen atom side hydrocarbon, the state of the salt formation is not changed by the measurement method. It can be measured.

On the other hand, in the case where the salt type block copolymer (P2) is a salt type block copolymer in which a salt is formed by the compound represented by the above general formula (1) or (3), the acidic group used for salt formation is used. The acid value was calculated by removing it. This is because the acidic group used for salt formation does not function as an acidic group which increases the acid value of the dispersing agent. Therefore, in the present invention, the acid value of the salt salt type block copolymer formed by the compound represented by the above general formula (1) or (3) is calculated from the value obtained by the following formula. When the acid value of the salt type salt block copolymer formed by the above general formula (1) or (3) is measured by the method described in the above-mentioned JIS K 0070, the salt formation state is changed. Can not determine the correct value.

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) for salt formation - the acid value consumed by salt formation} Salt formation of the acidity of the front block copolymer (P1)

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

Specifically, for example, a 13 C-NMR spectrum of a salt block copolymer is measured using a nuclear magnetic resonance apparatus, and the obtained spectral data is obtained by nitrogen at the terminal end portion and nitrogen having no salt formed. The ratio of the peak of the carbon atom adjacent to the atom and the integrated value of the peak of the carbon atom adjacent to the nitrogen atom forming the salt, and the ratio of the number of nitrogen sites at the end of the salt formation to the total number of nitrogen sites at the terminal is calculated. The ratio of the nitrogen content at the end of the formed salt calculated by the 13C-NMR spectrum (%) of the salt formed by the salt measured by the method described in JIS K 7237 (P1) }, calculate the amine price consumed, which is the same value as the acid value consumed by salt formation.

However, in the case where the compound represented by the above formula (1) forms a salt at a molar ratio of 1 mol or less with respect to 1 mol of the nitrogen moiety at the terminal of the structural unit represented by the general formula (I), The case where the compound represented by the above general formula (3) of the acidic group forms a salt in an amount of 1 mol or less, or the compound represented by the above general formula (3) having two acidic groups forms a salt at 0.5 mol or less, and is acidic. When the total amount of the base forms a salt with the nitrogen moiety at the end of the constituent unit represented by the general formula (I), since the acidic group does not affect the acid value in the salt type block copolymer after the salt formation, It can be made to have the same acid value as the block copolymer before salt formation.

On the other hand, when the compound represented by the above general formula (3) having two acidic groups is added in excess of the above molar number, since an acidic group having no salt is present in the dispersing agent after the salt is formed, Therefore, as described above, the acid which does not form a part of the acidic group of the salt The valence is added to the acid value of the block copolymer before salt formation, and the acid value of the dispersant is calculated.

Further, in the present invention, the glass transition temperature of the dispersant is 30 ° C or higher. That is, the dispersing agent has a glass transition temperature of 30 ° C or more regardless of the block copolymer (P1) or the salt block copolymer (P2).

When the glass transition temperature of the dispersant is less than 30 ° C, especially when the developer temperature (usually about 23 ° C) is equal to or lower than the developer temperature, the development adhesiveness is lowered. When the glass transition temperature is equal to or lower than the temperature of the developer, the movement of the dispersant during development becomes large, and as a result, the development adhesiveness is deteriorated.

The glass transition temperature of the dispersant is preferably 32 ° C or higher, more preferably 35 ° C or higher from the viewpoint of developing adhesion. On the other hand, from the viewpoint of operability when the fine scale is easily used, etc., it is preferably 200 ° C or lower.

The glass transition temperature of the dispersant in the present invention is determined by differential scanning calorimetry (DSC) according to JIS K 7121.

Among them, the glass transition temperature (Tg) of the block copolymer having no salt formation is calculated by the following formula and can be used as an index.

1/Tg=Σ(Xi×Tgi)

Here, the block copolymerization system is a copolymerization of n monomer components from i=1 to n. The weight fraction of the i-th monomer of Xi system (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, the lanthanum adopts the sum of i=1 to n. Further, the value (Tgi) of the glass transition temperature of the homopolymer of each monomer can be a value of Polymer Handbook (3rd Edition) (J. Brandrup, 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 the DSC described above, as shown in the examples below. An indicator of the glass transition temperature of a salt block copolymer.

In the color material dispersion liquid of the present invention, at least one of the block copolymer and the salt block copolymer is used as the dispersing agent, and the content thereof is blended with the type of the color material to be used, and further, color filter to be described later. The sheet is appropriately selected from the solid content concentration in the photosensitive colored resin composition and the like.

The content of the dispersant is preferably from 3 to 45 parts by mass, preferably from 5 to 35 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion. When it is more 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 superior. Moreover, when it is below the said upper limit, the developability is favorable.

In particular, in the case of forming a coating film or a colored layer having a high color material concentration, the content of the dispersing agent is preferably 3 to 25 parts by mass, more preferably 5 parts by mass based on 100 parts by mass of the total solid content in the color material dispersion liquid. ~20 parts by mass ratio to be blended.

Further, in the present invention, the solid portion is the owner other than the above solvent, and includes a monomer dissolved in a solvent or the like.

<color material>

In the present invention, the color material can be used to form a desired color when the colored layer of the color filter is formed, and the rest is not particularly limited, and various organic pigments, inorganic pigments, and dispersible dyes can be used alone or in combination. Used above. Among them, organic pigments are suitable for use because of their high color developability and high heat resistance. The organic pigment may, for example, be a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), and specifically has the following coloring index (C.I.).

CI 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 derivative pigments of CI Pigment Yellow 150; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49 , 51, 61, 63, 64, 71, 73; CI pigment purple 1, 19, 23, 29, 32, 36, 38; CI pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48 :3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63 : 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146 , 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI pigment blue 15, 15:3, 15:4, 15:6, 60; CI pigment green 7, 36, 58, 59; CI pigment brown 23, 25; CI pigment black 1, 7.

Among them, in the case of containing C.I. Pigment Green 59 as a color material, it is preferable from the viewpoint of obtaining a green color material dispersion liquid which exhibits greenish blue color, excellent color material dispersion stability, and high luminance. If the green color material dispersion is used, color filtering The green pixel of the film does not need to be thickened, and can be made into the chromaticity region of the above-mentioned high color density green, and high luminance or high contrast can be achieved. The C.I. Pigment Green 59 will be described in detail in the description of the second invention to be described later. Further, the derivative pigment of C.I. Pigment Yellow 150 is also described in detail in the description of the second invention to be described later.

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

For example, when the color material dispersion liquid of the present invention is used as a photosensitive coloring resin composition for a color filter to be described later to form a light-shielding layer pattern on a substrate of a color filter, a black having a high light-shielding property is blended in the ink. pigment. As the black pigment having high light-shielding property, for example, an inorganic pigment such as carbon black or triiron tetroxide or an organic pigment such as cyanine black can be used.

As the dispersible dye, for example, various substituents may be added to the dye, or a well-known lake formation method may be used, a solvent may be insolubilized to become a dispersible dye, or a combination of low solubility may be used. The solvent becomes a dispersible dye. By using such a dispersible dye in combination with the above dispersant, the dispersibility or dispersion stability of the dye can be improved.

As the dispersible dye, it can be suitably selected from conventional dyes. Examples of such a dye include an azo dye, a metal salt azo dye, an anthraquinone dye, and a triphenylmethane dye. Dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, phthalocyanine dyes, and the like.

Further, as a standard, when the amount of the dye dissolved is 10 mg or less based on 10 g of the solvent (or the mixed solvent), it can be judged that the solvent (or the mixed solvent) is the dye. Dispersible.

The average primary particle diameter of the color material used in the present invention is not particularly limited as long as it is a coloring layer of a color filter, and the color material used is not particularly limited. The type varies, but is preferably in the range of 10 to 100 nm, more preferably 15 to 60 nm. By setting the average primary particle diameter of the color material to the above range, it is possible to provide a display device including the color filter produced by using the color material dispersion liquid of the present invention with high contrast and high quality.

Further, the average primary particle diameter of the color material of the present invention means "the volume distribution medium diameter (D50)". The average primary particle size of the color material is based on Hitachi High Technologies Co., Ltd., electric field emission scanning electron microscope (S-4800), and a dedicated bright-field STEM stage and selective detector are installed, making it usable for scanning. A penetrating electron microscope (hereinafter referred to as "STEM"), taking a 200,000-fold STEM photograph, reading it into the following software, and randomly selecting 100 color materials on the photograph to measure the diameter (long diameter) by volume The distribution of the basis was found to be 50% cumulative particle size by volume.

The sample for the measurement of STEM is prepared by mixing a color material and toluene, and dropping it onto a patch of fire-cotton film. In addition, when the particle size distribution or the volume distribution diameter (D50) of the volume reference was obtained from the STEM photograph, the image analysis type particle size distribution measurement software "Mac-View Ver. 4" manufactured by Mountech Co., Ltd. was used.

Further, the average dispersed particle diameter of the color material in the color material dispersion liquid varies depending on the type of the color material to be used, but is preferably in the range of 10 to 100 nm, more preferably 15 to 60 nm.

The average dispersed particle diameter of the color material in the color material dispersion liquid is a dispersion particle diameter of the color material particles dispersed in the dispersion medium containing at least the solvent, and is measured by a laser light scattering particle size distribution meter. As a particle size measurement by a laser light scattering particle size distribution meter, it is a color The solvent used in the material dispersion is appropriately diluted with a color material dispersion to a concentration (for example, 1000 times or the like) which can be measured by a laser light scattering particle size distribution meter, and a laser light scattering particle size distribution meter (for example, NANOTRACK manufactured by Nikkiso Co., Ltd.) is used. The particle size distribution measuring apparatus UPA-EX150) was measured by a dynamic light scattering method at 23 °C. The average distribution particle diameter here is a volume average particle diameter.

The color material used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt polishing method. Moreover, the commercially available color material can also be used for miniaturization.

In the color material dispersion liquid of the present invention, the content of the color material is not particularly limited. The color material content is preferably from 5 to 80 parts by mass, more preferably from 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. Provisioning.

In particular, in the case of forming a coating film or a colored layer having a high color material concentration, it 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. Proportional allocation.

<solvent>

The solvent to be 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 be dissolved or dispersed. The solvent may be used alone or in combination of two or more.

Specific examples of the solvent include alcoholic solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxylated alcohol; methoxyethoxyethanol and ethoxyethoxyethanol; Carbitol solvent; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, hydroxyl Ethyl propionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, An ester solvent such as ethyl lactate or cyclohexanol acetate; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or 2-heptanone; methoxyethyl Acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate a glycol ether acetate solvent such as an ester; a card of methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA), etc. Alcohol acetate solvent; diacetate such as propylene glycol diacetate or 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether a glycol ether solvent such as diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether or dipropylene glycol dimethyl ether; N,N-dimethylformamidine An aprotic ether amine solvent such as an amine, N,N-dimethylacetamide or N-methylpyrrolidone; a lactone solvent such as γ-butyrolactone; and a cyclic ether solvent such as tetrahydrofuran; An unsaturated hydrocarbon solvent such as benzene, toluene, xylene or naphthalene; N-heptane, N-hexyl , N- octane of saturated hydrocarbon-based solvents; toluene, xylene and the like aromatic hydrocarbons such as the organic solvent. Among these solvents, a glycol ether acetate solvent, a carbitol acetate solvent, a glycol ether solvent, and an ester solvent are preferably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol acetic acid from the viewpoints of solubility or coating suitability of other components. a group consisting of ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate More than one type.

The color material dispersion liquid of the present invention is preferably in a range of from 55 to 95% by mass, more preferably from 65 to 90% by mass, based on the total amount of the color material dispersion liquid containing the solvent. More preferably, it is in the range of 70 to 88% by mass. When the amount of the solvent is too small, the viscosity increases and the dispersibility is liable to lower. Further, when the amount of the solvent is too large, the concentration of the color material is lowered, and it is difficult to achieve the target chromaticity coordinate.

<Other ingredients>

In the color material dispersion liquid of the present invention, the dispersion auxiliary resin and other components can be further prepared as needed without impairing the effects of the present invention.

The dispersing auxiliary resin may, for example, be an alkali-soluble resin exemplified as a photosensitive colored resin composition for a color filter to be described later. Since the steric hindrance of the alkali-soluble resin makes the color material particles hard to come into contact with each other, there is a case where the effect of the dispersing agent is reduced by dispersion stabilization or by a dispersion stabilizing effect.

Further, examples of the other component include a surfactant for improving wettability, a decane coupling agent for improving adhesion, an antifoaming agent, a shrinkage preventing agent, an antioxidant, an anti-aggregating agent, an ultraviolet absorber, and the like. .

The color material dispersion liquid of the present invention is used as a preliminary preparation for preparing a photosensitive coloring resin composition for a color filter to be described later. In other words, the color material dispersion liquid is prepared in a stage before the preparation of the photosensitive coloring resin composition for a color filter described later, (the mass of the color material component in the composition) / (other than the color material component in the composition) A relatively high color material dispersion of solid mass). Specifically, the ratio of (the mass of the color component in the composition) / (the mass of the solid component other than the color component in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid and each component described below, it is possible to prepare a photosensitive coloring resin composition for a color filter excellent in dispersibility.

<Method for Producing Color Material Dispersion>

In the present invention, the method for producing a color material dispersion liquid is a method of obtaining a color material dispersion liquid dispersed in a solvent by using the above-mentioned block copolymer or a dispersant of a salt type block copolymer. There is no special limit. Among them, the dispersion and dispersion of color materials From the viewpoint of excellent stability, it is preferably one of the following two production methods.

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

Further, in the second method for producing a color material dispersion liquid of the present invention in the case of using a dispersant which is a salt type block copolymer, the solvent, the block copolymer, and the general formula (1) are selected from the above (3) One or more kinds of the compound in the group are mixed with the color material, and at least a part of the nitrogen portion at the terminal end of the structural unit represented by the general formula (I) forms a salt with the compound, and the color is obtained. The step of material dispersion.

When a salt type block copolymer is used, according to the first production method described above, after preparing a salt type block copolymer, the salt type block copolymer is used as a dispersing agent to disperse the color material, so that it can be accurately It is preferable from the viewpoint of the reaction end point or the reaction rate of the block copolymer before the formation of the salt and the one or more compounds of the group consisting of the above general formulas (1) to (3).

Further, according to the second production method described above, the color material is dispersed under the dispersing agent for preparing the salt type block copolymer, so that the salt type block copolymer does not spontaneously aggregate, and the color material dispersion can be efficiently prepared. And can improve dispersion.

In the first manufacturing method and the second manufacturing method described above, the color material can be dispersed using a conventional disperser.

Specific examples of the dispersing machine include a roll mill such as a twin roll machine and a three roll machine, a ball mill such as a ball mill or a vibrating ball mill, a paint regulator, a continuous disc type bead mill, and a continuous ring type bead mill. Mill. The preferred dispersion conditions of the bead mill are preferably from 0.03 to 3.0 mm, more preferably from 0.05 to 2.0 mm.

Specifically, for example, a 2.0 mm second with a large bead diameter is used first. The zirconia balls were subjected to preliminary dispersion, and then 0.1 mm of zirconia balls having a small bead diameter were used for formal dispersion. Further, after dispersion, it is preferably filtered using a membrane filter of 0.5 to 2 μm.

I-2. First photosensitive photosensitive resin composition for color filter of the present invention

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

In the photosensitive coloring resin composition for a color filter of the present invention, the color material dispersion liquid according to the first aspect of the present invention is used, and the color material dispersion stability is excellent, and the development residue is suppressed. It has excellent adhesion and solvent resolubility, and it can form a comparatively excellent color layer.

The photosensitive colored resin composition for a color filter of the present invention contains at least a color material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, without impairing the effects of the present invention. Within the scope, other ingredients may be further included. In the following, the components contained in the photosensitive colored resin composition for a color filter of the present invention will be described. However, the dispersant, the color material, and the solvent are the same as those described in the above-described color material dispersion of the present invention. Therefore, the description is omitted here.

<alkali soluble resin>

The alkali-soluble resin of the present invention has an acidic group and can function as a binder resin, and is suitably selected for use in a developer which is used for pattern formation and which is particularly soluble in an alkaline developer.

A preferred alkali-soluble resin in the present invention is a tree having a carboxyl group as an acidic group. Specific examples of the lipid include an acrylic copolymer having a carboxyl group, a styrene-acrylic copolymer having a carboxyl group, and an epoxy (meth)acrylate resin having a carboxyl group. Among these, those having a carboxyl group in the side chain and further having an ethylenically unsaturated group in the side chain are preferred. The reason for this is that the film strength of the formed cured film can be enhanced by containing a photopolymerizable functional group. Further, these acrylic copolymers, styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination of two or more kinds.

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

Specific examples of the acryl-based copolymer having a carboxyl group include those described in JP-A-2013-029832, and specific examples thereof include methyl (meth)acrylate and ethyl (meth)acrylate. A monomer having no carboxyl group and a copolymer composed of one or more selected from the group consisting of (meth)acrylic acid and an acid anhydride thereof. In addition, a polymer obtained by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the copolymer and introducing an ethylenically unsaturated bond may be exemplified, but it is not limited thereto. This is the case.

Among these, an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group is added to the copolymer, and the like is particularly suitable from the viewpoints of sensitivity of the colored layer or film strength.

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, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film to the alkaline developer is lowered, and pattern formation is difficult. Again, if the copolymerization ratio When the amount is more than 50% by mass, when the image is developed by the alkali developer, the pattern tends to fall off or the surface of the pattern tends to be rough.

The preferred 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. If it is less than 1,000, the function of the binder after hardening is remarkably lowered, and when it exceeds 50,000, when patterning is performed by an alkaline developing solution, pattern formation may be difficult.

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

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

The epoxy compound, the monocarboxylic acid containing an unsaturated group, and the acid anhydride can be appropriately selected from known ones.

In the epoxy group (meth) acrylate resin having a carboxyl group, a structure (咔哚 structure) in which two benzene rings are bonded to the oxime skeleton represented by the following chemical formula (A) in the molecule is provided, and the display is improved. It is preferable from the viewpoint of improving the effect of suppressing the adhesion and improving the hardenability of the colored layer or the residual film ratio of the colored layer.

Epoxy (meth) propylene having a carboxyl group containing the above fluorene structure The correct mechanism of the acid ester resin (hereinafter referred to as "anthraquinone resin") has not been clarified, but it is considered that since the ruthenium skeleton contains a π-conjugated system, it is highly sensitive to radicals, and the oxime-based photoinitiator and oxime described later are combined. Tantalum resin can improve performance such as sensitivity, developability, and development adhesion. Further, since the oxime resin has high solvent resolubility, it is preferable from the viewpoint of designing a colorless resin composition having no agglomerates even at a high color density.

The oxime resin is preferably a polymerizable compound represented by the following general formula (B) described in JP-A-2007-119720, and an epoxy group having an anthracene skeleton described in JP-A-2006-308698. A reaction product (polycondensate) of a (meth) acrylate resin with a polybasic acid or the like.

(In the above general formula (B), X represents a group represented by the following general formula (D), and Y each independently represents a polyvalent carboxylic acid or an anhydride thereof, and R ⁱ represents a general formula (C) below. Base, j is an integer from 0 to 4, k is an integer from 0 to 3, and n is an integer greater than one.)

(In the above general formula (C), R ⁱⁱ represents a hydrogen atom or a methyl group, and R ⁱⁱⁱ each independently represents a hydrogen atom or a methyl group.)

[化8]

(In the above general formula (D), R ^iv each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and R ^v represents -O- or -OCH ₂ CH ₂ O- .)

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

The bisphenol compound can be exemplified by the above general formula (D), and R ^v is -O-, and this -O- is -OH.

As the bismuth bisphenol compound, for example, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis (4- Hydroxy-3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl) Indole, 9,9-bis(4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3, a bisphenol compound such as 5-dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene or the like, and mixtures thereof.

Examples of the polybasic acid and an acid anhydride thereof used for the reaction of the epoxy group (meth) acrylate resin having an anthracene skeleton include maleic acid, succinic acid, isaconic acid, citric acid, and tetrahydrofurfuric acid. a dicarboxylic acid such as hexahydrofurfuric acid, methyltetrahydrofurfuric acid, methyl endomethylenetetrahydrophthalic anhydride, chloro-bromic anhydride or glutaric acid or an anhydride thereof; biphenyltetracarboxylic acid, Phenyl ketone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, biphenyl sulfonium tetracarboxylic acid, 4-(1,2-dicarboxyethyl)-1,2,3,4-tetrahydronaphthalene-1, 2-dicarboxylic acid, butane tetracarboxylic acid, coke honey a tetracarboxylic acid such as a sulfuric acid or an acid dianhydride thereof; a tricarboxylic acid such as trimellitic acid or an acid anhydride thereof; or an anhydride thereof or the like. These may be used alone or in combination of two or more.

The oxime resin used in the present invention is preferably a ring having an anthracene skeleton which is an addition product of an anthracene epoxy (meth)acrylic acid derivative and a dicarboxylic acid anhydride and/or a tetracarboxylic dianhydride. An oxy (meth) acrylate acid adduct.

The commercially available product name of the oxime resin which can be used in the present invention is, for example, INR-16M (manufactured by Nagase ChemteX Co., Ltd.).

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

The alkali-soluble resin to be used for the photosensitive coloring resin composition for a color filter may be used singly or in combination of two or more kinds, and the content thereof is not particularly limited, and is sensitive to a color filter. The solid content of the colored resin composition is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass. When the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is more than the above upper limit, film roughness or pattern may occur during development. The situation of falling off. Further, in the present invention, the solid portion is a member other than the above solvent, and includes a liquid polyfunctional monomer or the like.

<Multifunctional monomer>

The polyfunctional monomer used in the photosensitive coloring resin composition for a color filter may be polymerizable by a photoinitiator to be described later, and is not particularly limited, and usually two or more may be used. The compound having an ethylenically unsaturated double bond is particularly preferably a polyfunctional (meth) acrylate having two or more acrylonitrile groups or methacryl groups.

Such a polyfunctional (meth) acrylate can be appropriately selected from known ones. Specific examples include those described in Japanese Laid-Open Patent Publication No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone or in combination of two or more. Further, when the photosensitive coloring resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer preferably has three (trifunctional) or more polymerizable double bonds. More preferably, the poly(meth) acrylate of a trihydric or higher polyhydric alcohol or the dicarboxylic acid modified product is specifically a trimethylolpropane tri(meth) acrylate, Pentaerythritol tri(meth) acrylate, pentaerythritol tri(meth) acrylate succinic acid modification, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate An ester, a succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like.

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

<Photoinitiator>

The photoinitiator used in the photosensitive coloring resin composition for a color filter is not particularly limited, and may be used alone or in combination of two or more kinds from various conventional photoinitiators. Specific examples include, for example, Japanese Patent Laid-Open No. 2013-029832 Reported by the reporter.

As the photoinitiator, one type may be used alone or two or more types may be used in combination. The photoinitiator is preferably an oxime ester photoinitiator from the viewpoint of suppressing the occurrence of pattern shedding and the effect of suppressing the occurrence of water bleeding. When a dispersing agent having an acid value is used, water bleeding tends to be particularly likely to occur, but it is suitably used from the viewpoint of suppressing the occurrence of water bleeding by using an oxime ester photoinitiator in combination. Further, the term "water infiltration" refers to a phenomenon in which, after alkali development, after rinsing with pure water, a trace such as water infiltration occurs. Since such water permeation disappears after post-baking, there is no problem as a product. However, when the appearance of the pattern surface is examined after development, an abnormality is detected, and the problem that the normal product and the abnormal product cannot be distinguished is generated. . Therefore, if the inspection sensitivity of the inspection apparatus is lowered at the time of visual inspection, the result is that the yield of the final color filter manufacturing is lowered, which is a problem.

As the oxime ester-based photoinitiator, it is preferable to reduce the contamination of the photosensitive coloring resin composition for a color filter or the device contamination by the decomposition product, and it is preferable to have an aromatic ring. In the case of having a condensed ring containing an aromatic ring, it is more preferred to have a condensed ring containing a benzene ring and a hetero ring.

As the oxime ester photoinitiator, it can be composed of 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzylidene)], ethyl ketone, 1-[9-B -6-(2-methylbenzhydryl)-9H-carbazol-3-yl]-, 1-(o-ethylidene oxime), Japanese Patent Laid-Open No. 2000-80068, JP-A-2001- An oxime ester photoinitiator described in, for example, 233842, JP-A-2010-527339, JP-A-2010- 527 338, and JP-A-2013-041153 is appropriately selected. As a commercially available product, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Corporation), ADEKA OPT-N-1919, ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-831 (above) ADEKA company), TR-PBG-304, TR-PBG-326, TR-PBG-3057 (the above is manufactured by Changzhou Power Electronic New Material Co., Ltd.).

The oxime ester-based photoinitiator used in the present invention is excellent in curability, and development resistance and pattern peeling occur in order to increase the color material concentration by using PG59 to achieve a wider color reproduction region. From the viewpoint of suppressing the effect of suppressing water and preventing the occurrence of water permeation, it is preferred to use an oxime ester photoinitiator which generates an alkyl radical, and more preferably an oxime ester light which generates a methyl radical. Starting agent. It is presumed that the alkyl radical is more likely to activate the radical movement than the aryl radical. As the oxime ester photoinitiator which produces an alkyl radical, for example, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl group ]-, 1-(o-ethenylhydrazine) (trade name: Irgacure OXE-02, manufactured by BASF), ketone, [8-[[(ethyloxy)imino][2-(2,2) ,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]oxazol-5-yl]-, (2,4,6 -trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(1,3-dioxolan, 4-(2-methoxy) Phenyloxy)-9H-carbazol-3-yl]-, 1-(o-ethenylhydrazine) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA), ketone, (9-ethyl- 6-nitro-9H-indazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-, o-ethenylhydrazine) (trade name) ADEKA AKLS NCI-831, manufactured by ADEKA), 1-propanone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl ]-, 1-(o-ethyl fluorenyl) (trade name: TR-PBG-304, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1-propanone, 3-cyclopentyl-1-[2-(2-pyrimidinesulfuric acid) ))-9H-carbazol-3-yl]-, 1-(o-ethyl fluorenyl) (trade name: TR-PBG-314, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ethyl ketone, 2-ring Hexyl-1-[2-(2-pyrimidinyloxy)-9H-indazol-3-yl]-,1-(o-ethylindenyl) (trade name TR-PBG-326, Changzhou Power Electronic New Material Co., Ltd. , ethyl ketone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-indazol-3-yl]-, 1-(o-ethylindenyl) (trade name TR-PBG) -331, Changzhou Power Electronics New Manufactured by Materials Co., Ltd., 1-octyl ketone, 1-[4-[3-[1-[(ethoxycarbonyl)imino]ethyl]-6-[4-[(4,6-dimethyl) 2-pyrimidinyl)thio]-2-methylbenzimidyl]-9H-carbazol-9-yl]phenyl]-, 1-(o-ethenylhydrazine) (trade name EXTA-9, UNION CHEMICAL company) and so on.

Further, in the oxime ester photoinitiator, it is preferred to use a photoinitiator having a tertiary amine structure in combination from the viewpoint of sensitivity improvement. The reason for this is that a photoinitiator having a tertiary amine structure has a tertiary amine structure belonging to an oxygen quencher in the molecule, so that the radical generated by the initiator is not easily deactivated by oxygen, and the sensitivity can be improved. Caused. As a commercially available product of the above-mentioned photoinitiator having a tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)diphenyl ketone (for example, Hicure ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), and the like.

The content of the photoinitiator used in the photosensitive colored resin composition for a color filter is not particularly limited, and the total amount of the solid content of the photosensitive colored resin composition for the color filter is higher than that of the photoinitiator. Preferably, it is in the range of 3 to 40% by mass, more preferably 10 to 30% by mass. When the content is less than the above lower limit, photohardening may not be sufficiently performed, and the exposed portion may be eluted during development; on the other hand, if it is more than the above upper limit, yellowing of the obtained colored layer becomes strong, The situation where the brightness is lowered.

<arbitrarily added ingredients>

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

As an additive, for example, an antioxidant, for example, a polymerization stopper, a chain A moving agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, a UV absorber, a dense adhesion promoter, and the like.

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-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and lanthanoid antioxidants, and are preferably blocked from the viewpoint of heat resistance. Phenolic antioxidants.

In the case of using an antioxidant, the amount of the antioxidant is not particularly limited, and the amount of the antioxidant is a solid content in the photosensitive colored resin composition for a color filter. The total amount of the antioxidant is preferably from 0.1 to 5.0% by mass, more preferably from 0.5 to 4.0% by mass. When it is more than the above lower limit value, heat resistance is excellent. On the other hand, the photosensitive colored resin composition for a color filter of the present invention can be used as a photosensitive resin composition for a high-sensitivity color filter.

Further, as a specific example of the surfactant and the plasticizer, for example, those described in JP-A-2013-029832 can be cited.

<Preparation ratio of each component in the photosensitive colored resin composition for color filters>

The total content of the color material is preferably a ratio of 3 to 65% by mass, more preferably 4 to 60% by mass, based on the total amount of the solid content of the photosensitive colored resin composition for a color filter. When the color filter is coated with a photosensitive colored resin composition to have a predetermined film thickness (usually 1.0 to 5.0 μm), the colored layer can have a sufficient color density. Moreover, when it is at most the above upper limit value, the storage stability is excellent, and a coloring layer having sufficient hardness or adhesion to the substrate can be obtained. Especially in the formation When the coloring layer having a high coloring material concentration is used, the coloring matter content is preferably adjusted to a ratio of 15 to 65% by mass, more preferably 25 to 60% by mass, based on the photosensitive colored resin composition for a color filter.

In addition, the content of the dispersing agent is not particularly limited as long as the coloring material can be uniformly dispersed. For example, the solid content of the photosensitive colored resin composition for a color filter can be 1 to 40 mass. %. In addition, the total 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 it is more 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. Moreover, when it is at most the above upper limit value, the developability is good. In particular, when a coloring layer having a high color material concentration is formed, the dispersant content is preferably adjusted to a ratio of 2 to 25% by mass, more preferably 3 to 20% by mass, based on the photosensitive colored resin composition for a color filter. Further, in the case of the salt type block copolymer, the mass of the dispersant is the block copolymer before salt formation and one or more compounds of the group consisting of the above general formulas (1) to (3). Total quality.

In addition, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high precision. The total amount of the photosensitive colored resin composition for the color filter containing the solvent is usually in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass. When the content of the solvent is within the above range, the coating property is excellent.

<Method for Producing Photosensitive Colored Resin Composition for Color Filter>

The method for producing the photosensitive colored resin composition for a color filter of the present invention is not particularly limited, and for example, alkali soluble can be added to the color material dispersion of the present invention. The resin, the polyfunctional monomer, the photoinitiator, and other components as needed can be prepared by mixing using a known mixing means.

I-3. First color filter related to the present invention

The first color filter according to the present invention is characterized in that at least one of a transparent substrate and a colored layer provided on the transparent substrate is characterized in that at least one of the colored layers has the first invention described above. The colored filter is formed by curing the photosensitive colored resin composition to form a colored layer.

The color filter related to 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. According to FIG. 1, the color filter 10 of the present invention includes a transparent substrate 1, a light shielding portion 2, and a coloring layer 3.

<Colored layer>

At least one of the coloring layers used in the color filter of the present invention is a coloring layer formed by curing the coloring filter composition of the color filter of the present invention.

The colored layer is usually formed in an opening of a light-shielding portion on a transparent substrate to be described later, and is usually composed of three or more colored patterns.

Further, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set.

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

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

First, the photosensitive coloring resin composition for a color filter of the present invention is applied to a later-described coating method 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. On the transparent substrate, a wet coating film is formed. Among them, spin coating or die coating is preferably used.

Next, the wet coating film is dried using a hot plate or an oven, and then exposed to a mask having a predetermined pattern to photopolymerize the alkali-soluble resin and the polyfunctional monomer to form a hardening. Coating film. 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 an electron beam. The exposure amount is appropriately adjusted depending on the thickness of the light source or coating film to be used and the like.

Further, in order to promote the polymerization reaction after the exposure, heat treatment may be performed. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition for the color filter to be used, the thickness of the coating film, and the like.

Next, development processing is carried out using a developing solution, and the unexposed portion is dissolved and removed to form a coating film in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. In the alkali solution, a surfactant or the like may be added in an appropriate amount. Further, the development method can be carried out by a general method.

After the development treatment, the developer is usually washed, and the colored filter is dried with a cured coating film of the photosensitive colored resin composition to form a colored layer. Further, after the development treatment, heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected in accordance with the use of the coating film.

<shading section>

The light-shielding portion of the color filter of the present invention is formed into a pattern on a transparent substrate to be described later, and can be used in the same manner as a light-shielding portion used in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape. The light shielding portion may be a metal thin film such as chromium formed by a sputtering method, a vacuum deposition method, 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 the resin adhesive. In the case of a resin layer containing light-shielding particles, there is a method of patterning by using a photosensitive resist by development, a method of patterning using an inkjet ink containing light-shielding particles, and heat-transfering a photosensitive resist. Printing method, etc.

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

<Transparent substrate>

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples thereof include a transparent rigid material that is not flexible such as quartz glass, an alkali-free glass, and a synthetic quartz plate, or a flexible transparent material such as a transparent resin film, an optical resin sheet, or a flexible glass.

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

Further, in the color filter of the present invention, in addition to the transparent substrate, the light shielding portion, and the coloring layer, for example, a protective layer or a transparent electrode layer, or even an alignment film, an alignment protrusion, a columnar spacer, or the like may be formed.

I-4. First liquid crystal display device related to the present invention

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

The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic view showing an example of a liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, an opposite substrate 20 having a TFT array substrate, and the like, and a surface between the color filter 10 and the opposite substrate 20. Liquid crystal layer 30.

Further, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2, and may be a configuration known as a liquid crystal display device used for a general color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be employed. Such a driving method may be, for example, a TN method, an IPS method, an OCB method, or an MVA method. In the present invention, any of these methods can be suitably used.

Moreover, it can be suitably selected and used as a counter substrate to which the liquid crystal display device of the present invention can be driven.

In addition, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies and mixtures thereof can be used in combination with the driving method of the liquid crystal display device of the present invention.

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

In the vacuum injection method, for example, a liquid crystal cell is prepared by using a color filter and a counter substrate in advance, an isotropic liquid is formed by heating the liquid crystal, and a liquid crystal is injected into the liquid crystal in an isotropic liquid state by a capillary effect. In the cell, a liquid crystal layer can be formed by performing sealing using an adhesive. Thereafter, the liquid crystal cell is slowly cooled to a normal temperature to align the sealed liquid crystal.

Further, in the liquid crystal dropping method, for example, a sealant is applied to the edge of the color filter, and the color filter is heated to a temperature at which the liquid crystal becomes an isotropic phase, and the liquid crystal is equated using a dispenser or the like. The color liquid is dropped, the color filter is superposed on the counter substrate under reduced pressure, and the liquid crystal layer is formed by adhering through a sealant. Thereafter, the liquid crystal cell is slowly cooled to a normal temperature to align the sealed liquid crystal.

I-5. First organic light-emitting display device related to the present invention

The organic light-emitting display device according to the first aspect of the invention is characterized by comprising the color filter of the present invention and an organic light-emitting body.

The organic light-emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic view showing an example of an 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-emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

As a method of laminating the organic light-emitting body 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the color filter. A method of bonding an organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60 or the like. The transparent anode 71 in the organic light-emitting body 80, the hole injection layer 72, the hole transport layer 73, and the light-emitting layer The layer 74, the electron injecting layer 75, the cathode 76, and other structures can be appropriately used. The organic light-emitting display device 100 thus produced is, for example, an organic EL display that can be applied to a passive driving method or an organic EL display that can be applied to an active driving method.

Further, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be a known structure of an organic light-emitting display device used as a general color filter.

II. Second invention

Hereinafter, the second color material dispersion liquid for color filters, the photosensitive coloring resin composition for color filters, the 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.

II-1. Second color material dispersion related to the present invention (i) Second embodiment of the present invention

The color material dispersion liquid for a color filter according to the first embodiment of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent, wherein the color material contains CI color green 59; The dispersant is a polymer having the following structural unit represented by the general formula (I).

(In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bond group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ³ They can also be bonded to each other to form a ring structure.)

In the color material dispersion liquid according to the first embodiment of the present invention, the color material contains CI Pigment Green 59 (hereinafter sometimes abbreviated as PG59), and an aggregate having a constituent unit represented by the general formula (I) is used in combination. As a result, a green color material dispersion liquid which exhibits greenish blue color, excellent dispersion stability of color materials, and high luminance can be obtained.

According to the second aspect of the invention, since PG59 is used as the color material, a chromaticity region which cannot be achieved by PG58 can be achieved, and a polymer having a constituent unit represented by the general formula (I) can be used in combination, so that high luminance can be achieved. A color filter that is highly contrasted and has a large triangle and excellent color reproducibility connected by three points of red, green, and blue pixels.

Further, in the color material dispersion liquid according to the first embodiment of the present invention, since a polymer having a constituent unit represented by the general formula (I) is used as a dispersing agent in combination with PG59, it is possible to produce a solvent having excellent dispersion stability and a solvent. A photosensitive colored resin composition having excellent resolubility. Since a polymer having a structural unit represented by the general formula (I) is combined as a dispersing agent in a color material containing PG59, it is estimated that the color material containing PG59 is strongly adsorbed to nitrogen contained in the constituent unit represented by the general formula (I). The color material is excellent in dispersibility of the coloring material, and the color material containing PG59 which is strongly adsorbed to the nitrogen portion and surrounded by the dispersing agent is easily washed away by the solvent having resolubility while being adsorbed to the dispersing agent. In addition, in the case where a polymer having a structural unit represented by the general formula (I) is combined as a dispersing agent in a color material containing PG59, the development residue tends to be suppressed. The reason for this is that the color material containing PG59 which is firmly adsorbed to the nitrogen portion and surrounded by the dispersing agent is easily removed by adsorption to the dispersing agent during development, and the color material is not left on the substrate, and the occurrence of development residue is easily suppressed. .

(ii) Second second embodiment of the present invention

The color material dispersion liquid for color filters according to the second embodiment of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent, wherein the color material contains CI color green 59 and The yellow color material; the dispersing agent may, for example, be a polymer having the structural unit represented by the above general formula (I).

In the color material dispersion liquid according to the second aspect of the present invention, the color material contains PG59 and a yellow color material, and a polymer having a structural unit represented by the general formula (I) is used in combination as a dispersing agent. The coloring layer which is excellent in dispersion stability of a color material, suppresses occurrence of display failure, and is excellent in high luminance and color reproducibility is formed.

In the second aspect of the invention, the PG59 which is a color material is used in a single color and exhibits a blueish green color, and the coloring power is strong and the luminance is high. Therefore, by combining with the yellow color material, even if the content of PG59 in the color material is suppressed, Or suppressing the P/V ratio ((the mass of the color component in the composition) / (the mass of the solid component other than the color component in the composition)), the green color contained in the green color region of the above high color density can still be produced. Picture. The green color material having a phthalocyanine skeleton is presumed to be poorly displayed in the green pixel. However, if the color material dispersion liquid of the present invention is used, the green color material having the phthalocyanine skeleton can be reduced in the pixel. Since the content is medium and the P/V ratio can be lowered, it is estimated that a green pixel which suppresses the occurrence of display failure can be achieved.

Further, in the second aspect of the present invention, PG59 as a color material can be used to achieve a chromaticity region which cannot be achieved by PG 58 in the green region of the high color density. Further, in the second embodiment of the present invention, the PG59 and the yellow color material are used in combination with the polymer having the structural unit represented by the general formula (I), so that the color material dispersibility and the color material dispersion are used. It is excellent in stability, and can be used as a color filter which achieves high luminance or high contrast, and has a large triangle connected by three points of red, green, and blue pixels and excellent color reproducibility.

Further, in the color material dispersion liquid according to the second embodiment of the present invention, since a polymer having a constituent unit represented by the general formula (I) is used as a dispersing agent in combination with PG59 and a yellow color material, solvent resolubility can be produced. Excellent photosensitive coloring resin composition. It is presumed that since the polymer having the structural unit represented by the general formula (I) is used as a dispersing agent for the combination of PG59 and the yellow color material, the PG59 and the yellow color material which are firmly adsorbed to the nitrogen portion and surrounded by the dispersing agent are easily adsorbed to the dispersion. The state of the agent is washed away by the solvent of resolubility.

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

In the color material dispersion liquid for a color filter according to the second embodiment of the present invention, the yellow color is easily formed by a coloring layer which is excellent in suppressing occurrence of display defects, high luminance and high contrast, and excellent color reproducibility. The color material is preferably selected from CI Pigment Yellow 138 (hereinafter sometimes abbreviated as PY138), CI Pigment Yellow 139 (hereinafter sometimes abbreviated as PY139), CI Pigment Yellow 185 (hereinafter sometimes abbreviated as PY185), and CI Pigment Yellow 150. (hereinafter sometimes abbreviated as PY150) and one or more of the group consisting of the derivative pigments.

In the color material dispersion liquid for color filters according to the second embodiment of the present invention, the color material is preferably at least one of C.I. Pigment Green 58 and C.I. Pigment Green 7 in addition to PG59. Among them, from the viewpoint of achieving the target chromaticity, suppressing the display failure, and forming a high-luminance green pixel, it is preferable to further contain PG58 in addition to PG59. On the other hand, from the viewpoint of achieving the target chromaticity, suppressing the display failure, and further reducing the P/V ratio and improving the plate-forming property such as development resistance, it is preferable to further contain PG7 in addition to PG59. Also, by achieving the target chromaticity, suppressing the display It is preferable to add PG58 and PG7 in addition to PG59 from the viewpoint of improving the brightness and improving the balance of the plate making property due to the decrease in the P/V ratio.

(iii) Second embodiment of the present invention

The color material dispersion liquid for color filters according to the third embodiment of the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent, and is characterized in that the color material is It contains CI Pigment Green 59, a blue color material, and a yellow color material; the yellow color material (Y1) contains at least one yellow color material of CI Pigment Yellow 185, or (Y2) contains CI Pigment Yellow 139 as an essential component, and further contains At least two kinds of yellow color materials of one or more of the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150 and its derivative pigments are selected, and the above-mentioned dispersing agent is, for example, a polymerization having the structural unit represented by the above general formula (I) body.

In the color material dispersion liquid according to the third embodiment of the present invention, the specific color material is contained, and a polymer having the structural unit represented by the above general formula (I) is used in combination as a dispersing agent, so that a color material can be formed. A coloring layer which is excellent in dispersion stability, suppresses occurrence of display defects, and has excellent high luminance and color reproducibility.

According to the second color material dispersion liquid according to the third embodiment of the present invention, it is estimated that the efficiency can be improved by combining either (Y1) or (Y2) of the yellow color material with PG59 and blue color material. It is preferable to reduce the total amount of the color material by the wavelength portion which is not sufficiently absorbed by the PG59 and the blue color material, and it is also possible to reduce the P/V ratio and reproduce the color. Therefore, in the greenness of the high color density, the region (x=0.14 to 0.30, y=0.61 to 0.75) belonging to the high color density green can be achieved, and further (x=0.14 to 0.30, y=0.66 to 0.75), and the suppression is performed. A color layer that exhibits poor brightness and forms high brightness.

In addition, when the specific yellow color material is combined with a specific dispersing agent to be described later, since the dispersibility is excellent, the contrast can be easily improved, and a photosensitive colored resin composition having excellent solvent resolubility can be produced.

In the color material dispersion liquid according to the third embodiment of the present invention, the blue color material preferably contains at least one of C.I. Pigment Blue 15:3 and C.I. Pigment Blue 15:4 from the viewpoint of luminance.

The second 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 insofar as the effects of the present invention are not impaired.

Hereinafter, each component of the second color material dispersion of the present invention will be described in detail.

<color material>

In the second aspect of the invention, the color material contains C.I. Pigment Green 59 which is a zinc phthalocyanine pigment.

PG59 is a chromaticity coordinate in the XYZ color system of JIS Z8701 which is measured by a single source and using a C light source, and can be expressed as a color material of x=0.10~0.30 and y=0.30~0.64, wherein x= 0.13~0.20 and y=0.32~0.60 are the characteristic color materials.

PG59 is represented by the XYZ colorimetric system of JIS Z8701 which is a single color and is measured by a C light source, and can be represented by an xy chromaticity coordinate region surrounded by the following Equations 1, 2 and 3.

(Equation 1) y=6.715×x-0.286

Where, in Equation 1, 0.121<x<0.133

(Equation 2) y=7147.200×x ⁵ -8466.000×x ⁴ +3891.400×x ³ -854.200×x ² + 86.380×x-2.579

Where, in Equation 2, 0.133<x<0.310

(Equation 3) y=1189.500×x ⁶ +1817.000×x ⁵ -3011.300×x ⁴ +1447.800×x ³ -307.420×x ² +27.628×x-0.285

Where, in Equation 3, 0.121<x<0.310

Among the xy chromaticity coordinate regions surrounded by the above equations 1, 2, and 3, the regions of x=0.13 to 0.20 and y=0.32 to 0.60 are the most characteristic and effective.

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

In order to coat the PG59 with a monomer and measure the color, a suitable dispersing agent, a binder component, and a solvent are prepared in PG59 to prepare a coating liquid, which is applied onto a transparent substrate, dried, and cured as necessary. As a binder component, a non-curable thermoplastic resin composition or a photocurable (photosensitive) or thermosetting resin may be used as long as a transparent coating capable of color measurement can be formed. Things. Further, in the photosensitive colored resin composition of the present invention to be described later, by using a composition containing only PG59 as a color material, a coating film containing only PG59 as a color material can be formed, and measurement can be carried out.

As a transparent coating film containing a dispersing agent and a binder component and capable of color measurement, for example, a transmittance of a light transmittance transmittance spectrum of a film thickness of 2.0 μm and a wavelength of 380 to 780 nm is 95%. As a standard.

Further, the spectroscopic transmittance spectrum can be measured using a spectroscopic measuring device (for example, a microscope device OSP-SP200 manufactured by Olympus). The measurement conditions are C light sources.

Further, in the color material dispersion liquid of the present invention, only PG59 alone may be used as the color material. On the other hand, before the effect of the present invention is not impaired, the color material different from PG59 exemplified in the color material item of the above-described first color material dispersion according to the present invention may be combined with PG59 as another color. material. As other color materials, for example, other green color materials, yellow color materials, or blue color materials are suitably used.

In the case of using the other color material different from PG59 in the color material dispersion liquid according to the second aspect of the present invention, the content ratio of PG59 is appropriately adjusted in accordance with the desired chromaticity, and is not particularly limited. In particular, it is preferable to contain 5% by mass or more of PG59, more preferably 10% by mass or more, based on the entire color material containing PG59 from the viewpoint of increasing the color reproducibility and increasing the luminance.

Further, in the second color material dispersion liquid according to the present invention, it is preferable to further use PG59 from the viewpoint of suppressing occurrence of display failure of green pixels and forming a color layer having high luminance and excellent color reproducibility. Yellow color material is used as the color material. (Second second embodiment of the present invention)

As the yellow color material, for example, CI 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 Derivative pigments of 152, 153, 154, 155, 156, 166, 168, 175, 185 and CI Pigment Yellow 150.

As a derivative pigment of C.I. Pigment Yellow 150, specifically, for example, a metal complex of a mono-, di-, tri-, and tetra-anion with a metal of the following formula (i) or a azo compound which is one of the tautomeric structures of at least one guest compound, as the above metal, For example, Li, Cs, Mg, Cd, Co, Al, Cr, Sn, and Pb are preferable, and Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn, and La are preferable. As the above-mentioned metal, Ni is more preferable, and it is more preferably at least one of the above-mentioned C.I. Pigment Yellow 150 derivative pigment containing Ni and Zn, and the C.I. Pigment Yellow 150 derivative pigment containing Ni and Cu. Among them, it is preferred that the ratio of Ni:Zn=8:2 to 2:8 (mole ratio) of the above-mentioned CI pigment yellow 150 derivative pigment containing Ni and Zn, and Ni:Cu=5:5~9.8 A ratio of 0.2 (mole ratio) of at least one of the above-mentioned CI Pigment Yellow 150 derivative pigments containing Ni and Zn.

(In the above chemical formula (i), R is independently an OH, NH ₂ , NH-CN, a mercaptoamine or an arylamine group, and R' is independently -OH or -NH ₂ .)

For the CI Pigment Yellow 150 and its derivative pigments, Japanese Patent Laid-Open Publication No. 2001-354869, JP-A-2005-325350, JP-A-2007-25687, JP-A-2007-23287, JP-A-2007- Obtained in Japanese Patent Publication No. 23288 and JP-A-2008-24927.

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

In the second color material dispersion of the present invention, the yellow color material is appropriately selected, and one type may be used alone or two or more types may be used in combination. As a better yellow color material, The same yellow color material is preferably used for the same reason as described for the photosensitive colored resin composition for a color filter to be described later.

Further, in the color material dispersion liquid according to the second embodiment of the present invention, the photosensitive coloring resin composition described later may be used in combination with PG59 and a yellow color material, without impairing the effects of the present invention. Other color materials. As other color materials, for example, other green color materials, blue color materials, orange color materials, and the like are suitably used. Examples of other green color materials different from PG59 include phthalocyanine green pigments such as PG58, PG7, and PG36. As the other preferred color material, it is preferable to use the same other color material for the same reason as described in the photosensitive coloring resin composition for a color filter to be described later.

In the second color material dispersion of the present invention, in the case where the other green color material is further contained, it is preferable to use a PY150 in combination with a yellow color material from the viewpoint of suppressing the occurrence of display defects and easily achieving a high luminance coloring layer. At least one of its derivative pigments and PY138.

In the color material dispersion liquid according to the second embodiment 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 use of PG59 and yellow color material and other color materials are used. The content ratio is preferably the same as the content ratio of the photosensitive colored resin composition described later. In addition, the coloring material dispersion liquid can be used in combination of two or more kinds to produce a photosensitive colored resin composition, and it is suitable to use it even if it is not the same ratio as the photosensitive colored resin composition mentioned later.

Further, in the second color material dispersion according to the present invention, the PG59 is combined with the blue color material and the yellow color material as the color material system, and the yellow color material is preferably (Y1) containing at least one yellow color material of PY185; Or (Y2) containing PY139 as an essential component, and further comprising a group consisting of a derivative pigment selected from PY138, PY150 and PY150 At least two kinds of yellow color materials (the second embodiment of the present invention).

In the case of the blue color material in the present invention, the spectral transmittance spectrum is measured in the same manner as described in the case of PG59, and a color material having a peak top in the range of 435 nm or more and 490 nm or less is used as a standard.

Examples of the blue color material include C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, and the like. Among the dyes which are dispersible as described in the photosensitive colored resin composition described later, a color material which is in the range of the above-mentioned blue color material is appropriately selected and used.

In the color material dispersion liquid according to the third embodiment of the present invention, the blue color materials are appropriately selected, and they may be used alone or in combination of two or more.

In the blue color material used in the third embodiment of the present invention, in the case where PG59 and the specific yellow color material are combined, the specific dispersion can be suppressed from the viewpoint of suppressing the decrease in luminance. From the viewpoint of superior dispersibility at the time of the agent, a β-type copper phthalocyanine pigment is preferable, and at least one of CI color blue 15:3 and CI color blue 15:4 is preferably contained, and these β-type copper ruthenium The cyanine pigment preferably contains 60% by mass to 100% by mass based on the total amount of the blue color material.

Among them, the blue color material is preferably at least one of C.I. Pigment Blue 15:3 and C.I. Pigment Blue 15:4 from the viewpoint of luminance.

In the third embodiment of the present invention, (Y1) contains at least one yellow color material of PY185, and may further contain other yellow color materials in addition to PY185, and as the yellow color material, for example, 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, Derivatives of 166, 168, 175 and PY150 Materials and so on.

In the third embodiment of the present invention, the yellow color material combined with the PY 185 is excellent in dispersion stability of the color material, suppresses occurrence of display failure, and is easy to achieve a color layer having high luminance and excellent color reproducibility. In other words, it is preferably one or more selected from the group consisting of PY139, PY150, and derivatives thereof.

In addition, in the third embodiment of the present invention, (Y2), PY139 is an essential component, and at least two kinds of yellow color materials selected from the group consisting of PY138, PY150, and derivative pigments thereof are further contained. In addition to the above-mentioned at least two kinds of yellow color materials, other yellow color materials may be further contained, and examples of the yellow color materials include PY1, 3, 12, 13, 14, 15, 16, 17, 20, and 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, and 175, and the like.

In the third embodiment of the present invention, in the case where the above (Y1) is used as the yellow color material, it is preferable because it is easy to achieve higher luminance. On the other hand, in the case where the above (Y2) is used as the yellow color material, it is preferable because it is easy to achieve high contrast.

In the third embodiment of the present invention, the above-mentioned (Y2) contains, as an essential component, PY139, and further contains at least two kinds of yellow color materials selected from the group consisting of PY138, PY150 and derivative pigments thereof. Among them, from the viewpoint of suppressing the occurrence of display defects and easily achieving a high-luminance and high contrast coloring layer, it is preferable to use PY139 as an essential component and further contain one or more selected from the group consisting of PY150 and its derivative pigments. At least 2 yellow color materials.

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

In the color material dispersion liquid according to the third embodiment of the present invention, the content ratio of each of the PG59, the blue color material, and the yellow color material, and the content ratio of the other color materials are preferably set to be sensitized later. The same ratio of content of the colored resin composition. In addition, since the coloring material dispersion liquid can be produced by appropriately mixing two or more kinds of the photosensitive coloring resin composition, it is suitable for use even if it is not contained in the same ratio as the photosensitive colored resin composition described later.

The average primary particle diameter of the color material used in the second invention or the average dispersed particle diameter of the color material in the color material dispersion liquid can be compared with the color material item in the color material dispersion liquid of the first invention described above. Since the description is the same, the description is omitted here.

Further, in the second color material dispersion liquid of the present invention, the color material content is the same as that described in the color material item in the color material dispersion liquid according to the first aspect of the present invention, and thus the description thereof will be omitted.

<dispersant>

In the second aspect of the invention, a polymer having the structural unit represented by the above general formula (I) is used as a dispersing agent. The constituent unit represented by the above general formula (I) is alkaline and plays a role The color material should be used as the function of the adsorption site.

The second color material dispersion liquid according to the present invention enhances the adsorption property to the color material by using a polymer having a structural unit represented by the general formula (I), and improves the dispersibility and dispersion stability of the color material.

The constituent unit represented by the above general formula (I) is the same as that described in the dispersant item in the color material dispersion liquid according to the first invention described above, and thus the description thereof will be omitted.

In the polymer having the structural unit represented by the above general formula (I), it is preferable to further improve the color material adsorption property, the color material dispersion stability, and the solvent resolubility in the salt formation site. A salt formed of at least a part of the nitrogen moiety at the terminal of the structural unit represented by the formula (I) and one or more compounds selected from the group consisting of the compounds represented by the following general formulas (1) to (3).

One or more compounds selected from the group consisting of the following general formulas (1) to (3) are the same as those described in the salt block copolymer article of the dispersant in the first color material dispersion of the present invention. Therefore, the description is omitted here.

(The symbols in the general formulas (1) to (3) are as described above.)

Further, in the dispersant used in the second aspect of the invention, the polymer having the structural unit represented by the general formula (I) is one or more selected from the group consisting of the general formulas (1) to (3). The content is in the color material dispersion related to the first invention of the above first Since the description of the salt block copolymer article of the dispersant is the same, the description thereof is omitted.

As the polymer having the structural unit represented by the general formula (I), it is more preferable to contain a solvent-affinitive site from the viewpoint of improving dispersibility. The solvent affinity site is preferably a solvent having an ethylenically unsaturated bond which is polymerizable with a monomer derived from a structural unit represented by the general formula (I), and a solvent having a solvent affinity. And choose the right one. As a standard, it is preferred to introduce a solvent affinity site so that the solubility of the polymer at 20 ° C is 20 (g/100 g solvent) or more with respect to the solvent used in combination.

The polymer having the structural unit represented by the general formula (I) used in the second aspect of the invention has high dispersibility and high density by improving the dispersibility and dispersion stability of the color material and the heat resistance of the resin composition. From the viewpoint of the color layer to be contrasted, among them, a block copolymer or a graft copolymer is preferred, and a block copolymer is particularly preferred. The following is a detailed description of the preferred block copolymer.

[block copolymer]

When a block containing the structural unit represented by the above general formula (I) is used as the A block, the A block is basic as shown in the above general formula (I), and functions as an adsorption site corresponding to the color material. function. In addition, at least a part of the nitrogen portion at the terminal of the structural unit represented by the general formula (I) is formed by forming a salt with at least one compound selected from the group consisting of the following general formulas (1) to (3). This salt forming unit functions as a stronger adsorption site for the relative color material. On the other hand, the B block which does not contain the structural unit represented by the above general formula (I) exhibits a function as a block having solvent affinity. Therefore, the block copolymer used in the present invention exhibits a function as a color material dispersing agent by the A block adsorbed on the color material and the B block having a solvent affinity.

The dispersant used in the second aspect of the invention is a block copolymer having the structural unit represented by the above general formula (I), and the amine copolymer of the block copolymer has an amine value of 40 mgKOH/g or more and 130 mgKOH/g or less. The dispersibility and dispersion stability of the pigment green 59 are preferable because they are more excellent.

In the dispersant used in the second aspect of the invention, the lower limit is preferably 50 mgKOH/g or more, more preferably 60 mgKOH/g or more from the viewpoint of dispersibility of the color material and dispersion stability. Further, the upper limit is preferably 120 mgKOH/g or less. When it is more than the above lower limit value, dispersion stability is more excellent. Moreover, when it is at most the above upper limit value, compatibility with other components is excellent, and solvent resolubility is good.

The amine valence in the case of the salt type block copolymer is smaller than the value of forming the salt only in the block copolymer before salt formation. However, since the salt-forming portion is a color material adsorption site which is similar to or stronger than the terminal nitrogen portion corresponding to the amine group, there is a tendency that the color material dispersibility or the color material dispersion stability is improved by salt formation. Further, the salt formation site is similar to the amine group, and if it is too large, it adversely affects the solvent resolubility. Therefore, in the present invention, the amine valence of the block copolymer before salt formation can be used as an index for improving the dispersion stability and solvent resolubility of the color material. The amine value of the obtained salt type block copolymer (P2) is preferably 0 mgKOH/g or more and 130 mgKOH/g or less, more preferably 0 mgKOH/g or more and 120 mgKOH/g or less.

When it is at most the above upper limit value, compatibility with other components is excellent, and solvent resolubility is good.

{A block}

The A block contains the block of the structural unit represented by the above general formula (I), and the structural unit represented by the above general formula (I) is as described above, and thus the description thereof is omitted.

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

The constituent unit represented by the general formula (I) may be a function of a color material adsorption site, and may be composed of one type or two or more constituent units.

The A block may have a constituent unit other than the constituent unit represented by the general formula (I) within the range which achieves the object of the present invention, and is a constituent unit which can be copolymerized with the constituent unit represented by the general formula (I). Can contain. For example, the constituent unit other than the constituent unit represented by the general formula (I) which may be contained in the basic block portion, for example, a constituent unit represented by the general formula (II) to be described later is exemplified.

In the A block in the block copolymer before salt formation, the content ratio of the constituent unit represented by the general formula (I) is preferably 50 to 100% by mass based on the total mass of the total constituent units of the A block. More preferably 80 to 100% by mass, and most preferably 100% by mass. This is because the higher the proportion of the constituent units 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. Further, the content ratio of the above-mentioned constituent units is calculated from the mass of the filling when the A block having the structural unit represented by the general formula (I) is synthesized.

Further, in the block copolymer before salt formation, the content ratio of the constituent unit represented by the general formula (I) is a total constituent unit with respect to the block copolymer, from the viewpoint that the dispersibility and the dispersion stability are good. The total mass is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. Moreover, the content ratio of each constituent unit in the above-mentioned block copolymer is calculated from the packing quality in the case of the block copolymer before the formation of the synthetic salt.

In addition, the constituent unit represented by the general formula (I) may have an affinity with the color material, and may be composed of one type or two or more constituent units.

{B block}

The B block system does not contain a block of the structural unit represented by the above general formula (I). The B block is preferably a monomer which is copolymerizable with a monomer derived from a structural unit represented by the general formula (I) and has an unsaturated double bond, and is appropriately selected as a solvent-compatible solvent. use. As a standard, it is preferred to introduce a B block so that the solubility of the copolymer at 23 ° C is 20 (g / 100 g solvent) or more with respect to the solvent to be used in combination.

The constituent unit constituting the B block may, for example, be a monomer having an unsaturated double bond copolymerizable with a monomer derived from a structural unit represented by the general formula (I), and among them, the following general formula (II) is preferred. ) The constituent units shown.

The constituent unit represented by the following general formula (II) can be the same as those described in the dispersant item in the color material dispersion liquid according to the first invention described above, and thus the description thereof will be omitted.

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

The number of constituent units constituting the B block is not particularly limited, and is preferably from 10 to 300, more preferably from 10 to 100, from the viewpoint of effective action of the solvent affinity portion and the color material adsorption portion and improvement of dispersibility of the color material. More preferably 10~70.

In the B block of the block copolymer, the content ratio of the constituent unit represented by the above general formula (II) is based on the total constituent unit of the B block from the viewpoint of enhancing the solvophilic property or the dispersibility of the color material. Total quality, preferably 50 to 100% by mass, more Good 70~100% by mass. Further, the content ratio of the above constituent units is calculated from the filling quality at the time of synthesizing the B block.

Further, in the block copolymer before salt formation, the content ratio of the constituent unit represented by the above general formula (II) is based on the total composition of the block copolymer from the viewpoint of improvement in dispersibility of the color material or dispersion stability. The total mass of the unit is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. Further, the content ratio of the above constituent units is calculated from the filling quality at the time of synthesis of the block copolymer before salt formation.

The B block may be appropriately selected from the constituent units in such a manner as to function as a solvophilic moiety, and the constituent unit represented by the above general formula (II) may be composed of one type or two or more constituent units. The two or more constituent units contained in the B block may be randomly arranged in the block.

In addition, by using the dispersant described below, the dispersion property of the color material is excellent, the effect of suppressing the occurrence of development residue is excellent, the solvent resolubility is excellent, and the coloring resin composition is high. It is preferable from the viewpoint of developing adhesion, and the dispersant is at least one of the following block copolymer (P1) and the following salt block copolymer (P2); P1: has the above general formula a block copolymer of the A block of the structural unit (I) and a B block of a constituent unit derived from the carboxyl group-containing monomer; and P2: a structural unit represented by the above general formula (I) of the block copolymer a salt type block copolymer having at least a part of a nitrogen moiety at a terminal end and a salt formed from at least one compound selected from the group consisting of the compounds represented by the above general formulas (1) to (3); an acid value of the dispersant When it is 1 mgKOH/g or more and 18 mgKOH/g or less, the glass transition temperature of this dispersing agent is 30 degreeC or more.

If the concentration of the color material is increased and the content of the dispersant is increased, the bonding dose is relatively reduced. Since it is few, the colored resin layer is easily peeled off from the base substrate at the time of development. The dispersing agent enhances the developing adhesiveness by containing a B block containing a constituent unit derived from a carboxyl group-containing monomer and having the above specific acid value and glass transition temperature. If the acid value is too high, it is presumed that although the developability is excellent, the polarity is too high, and peeling tends to occur at the time of development.

Such a dispersing agent can be the same as those described for the dispersing agent item used in the color material dispersion liquid according to the first invention described above, and thus the description thereof will be omitted.

In the color material dispersion liquid according to the second aspect of the invention, at least one type of polymer having the structural unit represented by the above general formula (I) is used as the dispersing agent, and the content thereof is blended with the type of the color material used, and further The color filter to be described later is appropriately selected from the solid content concentration in the photosensitive colored resin composition.

In the second color material dispersion liquid according to the present invention, the content of the dispersing agent can be the same as that described for the dispersing agent used in the color material dispersion liquid according to the first aspect of the present invention, and thus the description thereof will be omitted.

In the second color material dispersion liquid according to the present invention, the solvent to be used, the content thereof, other components which can be formulated as needed, and the method for producing the color material dispersion liquid can be related to the color of the first invention described above. Since the material dispersion is the same, the description thereof is omitted here.

In the second color material dispersion liquid according to the present invention, a preliminary preparation for modulating a photosensitive coloring resin composition for a color filter according to the second aspect of the present invention is used. In other words, the color material dispersion liquid is prepared in a pre-stage of preparing a photosensitive coloring resin composition for a color filter to be described later (the color component quality in the composition) / (the color material in the composition) A relatively high color material dispersion of solids other than the ingredients. Specifically, the ratio of (the mass of the color component in the composition) / (the mass of the solid component other than the color component in the composition) is usually 1.0 or more. Second invention phase In the color material dispersion liquid, a photosensitive coloring resin composition for a color filter according to the present invention, which is excellent in dispersibility, can be prepared by mixing the components described later.

II-2. Second photosensitive photosensitive resin composition for color filters according to the present invention (i) Second embodiment of the present invention

The photosensitive colored resin composition for a color filter according to the first embodiment of the present invention contains a color material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. The color material contains CI Pigment Green 59; and the dispersant is a polymer having the structural unit represented by the above general formula (I).

According to a second aspect of the present invention, in the photosensitive colored resin composition for a color filter, the color material contains CI color green 59, and the green color region of the high color density can be formed and formed. A coloring layer with high brightness or high contrast can be achieved. The photosensitive colored resin composition for a color filter according to the first embodiment of the present invention is the same as that described in the second embodiment of the present invention. The effect is to form a coloring layer having superior solvent resolubility, high luminance, high contrast, and excellent color reproducibility.

(ii) Second second embodiment of the present invention

The second photosensitive photosensitive resin composition for a color filter according to the second embodiment of the present invention contains a color material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. It is characterized in that the color material contains CI Pigment Green 59 and a yellow color material, and the dispersant may, for example, be a polymerization unit having a structural unit represented by the following general formula (I). body.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, the color material contains CI Pigment Green 59 and a yellow color material, and a combination unit having a general formula (I) is used in combination. Since the polymer is a dispersant, it is possible to form a color material having excellent dispersion stability and display failure by the same action as that described in the second color material dispersion liquid of the second embodiment of the present invention. A coloring layer that suppresses and has high luminance and color reproducibility.

(iii) Second embodiment of the present invention

The photosensitive colored resin composition for a color filter according to the third embodiment of the present invention is a color material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent. A photosensitive colored resin composition for a color filter, wherein the color material contains CI Pigment Green 59, a blue color material, and a yellow color material; and the yellow color material (Y1) contains at least one of CI Pigment Yellow 185 The yellow color material or (Y2) contains CI Pigment Yellow 139 as an essential component, and further contains at least two kinds of yellow color materials selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150, and derivative pigments thereof; The dispersing agent may, for example, be a polymer having a structural unit represented by the following general formula (I).

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the color material contains the CI color green 59, the blue color material, and the specific yellow color material, and the combination is used in the above-mentioned general manner. The polymer of the constituent unit represented by the formula (I) is used as a dispersing agent, and thus the third embodiment of the present invention according to the second aspect described above In the same manner as described in the color material dispersion liquid, it is possible to form a coloring layer which is excellent in dispersion stability of a color material, suppresses occurrence of display failure, and is excellent in high luminance and color reproducibility.

The second photosensitive coloring resin composition for a color filter according to the present invention contains at least a color material, a dispersing agent, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and is not damaged. Further, other components may be contained within the scope of the effects of the present invention. In the following, each component contained in the photosensitive colored resin composition for a color filter of the second aspect of the present invention will be described. However, CI Pigment Green 59 and a dispersant which are essential components among the color materials are the same as the above second. Since the description of the color material dispersion liquid of the present invention is the same, the description thereof will be omitted. Further, the solvent can be the same as those described in the above-described first color material dispersion of the present invention, and thus the description thereof will be omitted. Further, the alkali-soluble resin, the polyfunctional monomer, the photoinitiator, and other components may be the same as those described for the photosensitive coloring resin composition for a color filter of the first aspect of the present invention. The description is omitted.

<color material>

The second color material of the photosensitive coloring resin composition for a color filter according to the present invention contains C.I. Pigment Green 59 as an essential component. However, in order to adjust the color tone, other color materials may be further used in combination.

In the case of forming a colored layer of a color filter, it is not particularly limited as long as it can produce a desired color, and various organic pigments, inorganic pigments, and dispersible dyes may be used alone or in combination of two or more. Among them, organic pigments are suitable for use because of their high color developability and high heat resistance. The organic pigment may, for example, be a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), and specifically has the following coloring index (C.I.) number.

As the other color material, a color material different from PG59 as exemplified in the color material item of the above-described first color material dispersion according to the present invention may be used as the other color material. Among them, yellow color materials, other green color materials, and blue color materials are suitable.

Further, in the photosensitive coloring resin composition for a color filter according to the second aspect of the present invention, it is preferable from the viewpoint of suppressing the occurrence of display failure of green pixels and forming a color layer having high luminance and excellent color reproducibility. The LG59 is further combined with a yellow color material as a color material. (Second embodiment of the second invention). The yellow color material used in the second embodiment of the present invention as in the second embodiment can be the same as those described in the second color material dispersion liquid according to the second embodiment of the present invention. As the other color material used in the second embodiment of the present invention, it is preferable to use other green color materials, blue color materials, and orange color materials.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, it is preferable that at least one of PG58 and PG7 is contained in addition to PG59. Among them, PG58 is preferably contained in addition to PG59 from the viewpoint of achieving a target chromaticity, suppressing display failure, and forming a high luminance green pixel. When PG59 and PG58 are used in combination, color reproduction can be broadened, the above P/V ratio can be reduced, and luminance can be improved as compared with PG58 alone. On the other hand, from the viewpoint of achieving the target chromaticity, suppressing display failure, and further reducing the P/V ratio and improving the plate-forming property such as development resistance, it is preferable to further contain PG7 in addition to PG59. Moreover, it is preferable to further contain PG58 and PG7 in addition to PG59 from the viewpoint of achieving the target chromaticity, suppressing the display failure, improving the luminance, and reducing the balance of the P/V ratio and the plate-making property.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, the content ratio of PG59 to the entire color material can be matched. It is not particularly limited as long as it is necessary to adjust the chromaticity. In particular, from the viewpoint of suppressing occurrence of display failure, increasing color reproducibility, and improving luminance, it is preferable to contain 5 to 95% by mass of PG59, more preferably 10 to 90% by mass based on the entire color material containing PG59. More preferably, it is 20 to 80% by mass.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, the content ratio of the yellow color material to the PG59 is appropriately adjusted in accordance with the desired chromaticity, and is not particularly limited. . In the above, from the viewpoint of suppressing the occurrence of display failure and increasing the color reproducibility and increasing the luminance, it is preferable to contain 10 to 900 parts by mass, more preferably 20 to 400, of the yellow color material with respect to 100 parts by mass of PG59. Parts by mass.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, the yellow color material may be used singly or in combination of two or more kinds, and the display may be easily suppressed. From the viewpoint of a coloring layer having a poor occurrence, a high luminance, and a high contrast and excellent color reproducibility, it is preferably one or more selected from the group consisting of PY138, PY139, PY185, PY150, and derivative pigments thereof.

In a second embodiment of the present invention, PY150 and its derivative pigment are preferably used in a chromaticity region represented by y=0.550 to 0.610 and x=0.205 to 0.324, in the above chromaticity region. It is more preferable to reduce the above P/V ratio more easily.

Moreover, PY138 is preferably used for achieving high luminance in a chromaticity region of y=0.550~0.610 and x=0.205~0.324, wherein it is preferably used in a chromaticity region of x=0.246~0.324. High brightness situation.

Moreover, the PY185 is suitable for augmented color reproduction domain. In the case of y=0.610~0.626, it is also suitable for the chromaticity region expressed as x=0.205~0.324, and is more preferably used in It is expressed as a chrominance region of y=0.659.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, when at least one of PY150 and its derivative pigment is used in combination with PY138, the desired color is blended. The brightness, the film thickness and the film thickness may be appropriately adjusted. Preferably, the total amount of at least one of PY150 and its derivative pigments and the ratio of PY138 to 5:95 to 95:5. Among them, from the viewpoint of the luminance and the P/V ratio, the total amount of at least one of PY150 and its derivative pigments and the ratio of PY138 are preferably 10:90 to 90:10, and the luminance and P/V. From a point of view, it is even better at 20:80~80:20.

Further, in the case of the photosensitive coloring resin composition for a color filter according to the second embodiment of the present invention, when the green color material other than PG59 is further contained, the green color material containing PG59 is used for the entire color material. The content ratio can be appropriately adjusted in accordance with the desired color, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display failure, augmenting color reproducibility, and increasing the luminance, it is preferable to contain 10 to 90% by mass, more preferably 20 to 80% by mass, of the green color material containing PG59 for the entire color material. .

Further, the content ratio of the yellow color material to the green color material containing PG59 can be appropriately adjusted in accordance with the desired chromaticity, and is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display failure, augmenting color reproducibility, and increasing the luminance, it is preferable to contain 10 to 900 parts by mass, more preferably 20%, of the yellow color material with respect to 100 parts by mass of the green color material containing PG59. 400 parts by mass.

Further, in the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, when at least one of PG58 and PG7 is further contained, it is preferable to use the entire green color material containing PG59. Containing at least one of PG58 and PG7 in an amount of 5 to 50% by mass, wherein the ratio of display defects and luminance to the above P/V ratio From the viewpoint of the above, it is more preferably 5 to 40% by mass, and more preferably 5 to 30% by mass from the viewpoint of the luminance and the above P/V ratio.

Further, in the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, the color material may further contain a green color material and yellow in a range that does not impair the effects of the present invention. The color material other than the color material, the total content of the green color material containing PG59 and the yellow color material is preferably 70 to 100% by mass, and more preferably 80 to 100% by mass based on the entire color material.

Further, in the photosensitive coloring resin composition for a color filter according to the second aspect of the present invention, the blue color material and the yellow color material are combined as a color material in the PG59; and the yellow color material (Y1) contains the CI color yellow 185. At least one yellow color material or (Y2) contains CI Pigment Yellow 139 as an essential component, and further contains at least two kinds of one or more selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150, and a derivative pigment thereof. Yellow color material (second third embodiment of the present invention). The blue color material and the specific yellow color material used in the third embodiment of the present invention, which is the second embodiment of the present invention, can be the same as those described in the second color material dispersion liquid according to the third embodiment of the present invention. As the other color material used in the third embodiment of the present invention, it is preferable to use another green color material or an orange color material.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the target chromaticity is achieved, the display failure is suppressed, the P/V ratio is further reduced, and the development residue is suppressed. From the viewpoint of improving the development adhesiveness and the plate-making property, it is more preferable to contain PG7.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the content ratio of PG59 to the entire color material can be appropriately adjusted in accordance with the desired chromaticity, and is not particularly limited. Among them, by suppressing display failure, From the viewpoint of increasing the color reproducibility and improving the luminance, it is preferable to contain 5 to 80% by mass of PG59, more preferably 10 to 70% by mass, and even more preferably 10 to 60%, based on the entire color material containing PG59. %.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the content ratio of the blue color material to the PG59 is appropriately adjusted in accordance with the desired chromaticity, and is not particularly limited. . Among them, from the viewpoint of suppressing occurrence of display failure and increasing color reproducibility and increasing luminance, it is preferable to contain 10 to 300 parts by mass, more preferably 20 to 200 masses, of blue color material with respect to 100 parts by mass of PG59. Share.

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

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the content ratio of the yellow color material to the PG59 is appropriately adjusted in accordance with the desired chromaticity, and is not particularly limited. . Among them, from the viewpoint of suppressing occurrence of display defects and increasing color reproducibility and increasing luminance, it is preferable to contain 10 to 800 parts by mass, more preferably 20 to 600 masses, of yellow color material with respect to 100 parts by mass of PG59. Share.

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

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the content ratio of the yellow color material to the blue color material may be appropriately adjusted in accordance with the desired chromaticity, and Specially limited. In the above, from the viewpoint of suppressing the occurrence of display failure and increasing the color reproducibility and increasing the luminance, it is preferable to contain 10 to 800 parts by mass, more preferably 20%, of the yellow color material with respect to 100 parts by mass of the blue color material. 600 Parts by mass.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, when (Y1) at least one yellow color material containing CI Pigment Yellow 185 is used, PY185 is relative to yellow color material. The total amount is preferably from 10 to 100% by mass, more preferably from 20 to 100% by mass. PY185 has a strong coloring power, and has an effect of reducing the above P/V ratio even when it is contained in an amount of about 10% by mass based on the total amount of the yellow color material.

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

Further, in the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, CI pigment yellow 139 is used as an essential component (Y2), and further, it is selected from CI Pigment Yellow 138, CI. In the case of at least two kinds of yellow color materials of the group consisting of Pigment Yellow 150 and its derivative pigments, 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 material. %. In addition, the content of one or more selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150 and its derivative pigment 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), from the viewpoint of suppressing the occurrence of display failure and easily achieving a high-luminance and high contrast coloring layer, PY139 is preferably an essential component, and further contains a pigment selected from PY150 and its derivative pigments. At least two yellow color materials of one or more types of the group. Further, (Y2), when PY139 and at least two kinds of yellow color materials selected from the group consisting of PY150 and its derivative pigments are combined with the PG59 and the blue color material, the P can be further reduced. /V ratio, suppression of development residue, It is preferable from the viewpoint of improving the development adhesiveness and the plate making property.

In the above combination, from the viewpoint of improving the luminance and easily reducing the P/V ratio, it is preferable to use PY139 as an essential component and further contain at least two yellow color materials of a nickel-containing complex PY150 derivative pigment.

(Y2), in the case of combining PY139 and one or more selected from the group consisting of PY150 and its derivative pigments, from the viewpoint of easily achieving a high luminance and high contrast coloring layer, it is preferably selected from PY150. The content of one or more of the groups of the pigments of the derivative and the pigment thereof is more than the content of PY139, more preferably 150 to 700 parts by mass, still more preferably 200 to 600 parts by mass, per 100 parts by mass of PY139.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the specific yellow color material is appropriately selected, and one type may be used alone or two or more types may be used in combination.

In the second aspect of the invention, the PY185 is suitable for augmenting the color reproduction region, and is preferably used for the case of the chromaticity region of y=0.610 to 0.720 and x=0.140 to 0.230, and further to y=0.720 to 0.750. In the case, it is preferably used for the case where the chromaticity region of x=0.140 to 0.210 is expressed.

Further, PY139 is preferably used to display a chromaticity region of y=0.570 to 0.710 and x=0.180 to 0.265.

Further, in the case of the photosensitive coloring resin composition for a color filter according to the third embodiment of the present invention, when the green color material other than PG59 is further contained, the green color material containing PG59 is integrated with the entire color material. The content ratio can be appropriately adjusted in accordance with the desired color, and is not particularly limited.

In the case of further containing a green color material other than PG59, the content ratio of the green color material containing PG59 to the entire color material and the blue color material are contained. The content ratio of the green color material of 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 ratio of the content of the PG59 to the entire color material, the content ratio of the blue color material to the PG59, the content ratio of the blue color material to the entire color material, the content ratio of the yellow color material to the PG59, and the yellow color material, respectively. The content ratio of the entire color material is the same.

Further, in the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, when PG7 is further contained, the total amount of the green color material containing PG59 is preferably 5 to 50. PG7 of % by mass, more preferably from 5 to 45% by mass, from the viewpoint of display failure and luminance and the above P/V ratio.

Further, in the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the color material may further contain a green color material or a blue color in a range that does not impair the effects of the present invention. The total content of the green color material, the blue color material, and the specific yellow color material of the PG59 other than the color material and the yellow color material is preferably 70 to 100% by mass, more preferably the entire color material. 80 to 100% by mass.

In the photosensitive colored resin composition for a color filter of the second aspect of the present invention, the P/V ratio ((the mass of the color component in the composition) / (the mass of the solid component other than the color component in the composition) From the viewpoint of degassing or heat shrinkage, it is preferably 0.1 or more, more preferably 0.2 or more; on the other hand, it is excellent in display failure and ease of manufacture, that is, solvent resolvability, development residue, and development adhesion. From the viewpoint of excellent properties such as properties, development resistance, and effect of suppressing the occurrence of water bleeding, it is preferably 0.7 or less, more preferably 0.6 or less, 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 present invention, it is preferable that the chromaticity coordinate in the XYZ color system of JIS Z8701 which can be formed by using the C light source is A cured film in the range of x=0.180~0.330 and y=0.500~0.750.

In the second aspect of the present invention, the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention can be formed in the XYZ color of JIS Z8701 which is measured using a C light source. The chromaticity coordinates in the system are preferably in the range of x=0.188~0.324 and y=0.550~0.750, and the cured film in the range of x=0.200~0.324 and y=0.570~0.750 is better, x The cured film in the range of =0.205 to 0.324 and y = 0.580 to 0.750 is optimal.

In the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention, the XYZ color of JIS Z8701 is measured using a C-light source with a film thickness of 2.8 μm or less and a single pixel. Among the chromaticity coordinates in the system, the color space can be expressed as x=0.200~0.300, y=0.570~0.750, and the stimulus value Y is 37≦Y, and the better can be expressed as x=0.200~0.300. , y = 0.570 ~ 0.750 and the stimulus value Y is the color space of the range of 40 ≦ Y.

a good blending ratio or combination of the color space which can be expressed as a range of 37 ≦ Y, the total content of the color materials is 20 to 45 mass% with respect to the total solid content of the photosensitive colored resin composition for a color filter; As a combination in the color material, the content 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 ratio of PG59 to the green color material (G) containing PG59 is preferably 30% by mass or more. In addition, the film thickness of the cured film is applied and dried with a photosensitive colored resin composition, and then exposed and cured, and then post-baked in a dust-free oven at 230 ° C for 30 minutes. Film thickness.

In the second embodiment of the photosensitive coloring resin composition for a color filter according to the third embodiment of the present invention, it is preferable that the chromaticity coordinate in the XYZ color system of JIS Z8701 which is measured using a C light source is x= A cured film in the range of 0.140 to 0.330 and y = 0.50 to 0.750.

In the second aspect of the present invention, the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention can form an XYZ color system of JIS Z8701 which is measured using a C light source. The chromaticity coordinates in the range of x=0.140 to 0.280 and y=0.570 to 0.730 are preferable, and the cured film in the range of x=0.140 to 0.265 and y=0.610 to 0.720 is more preferable. It is preferable to form a cured film in the range of x=0.180 to 0.230 and y=0.690 to 0.710.

In the cured film of the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the film thickness is 2.8 μm or less, and the color measured by the C light source is measured by a single pixel, JIS Z8701. In the chromaticity coordinates in the XYZ color system, it is preferable to display a color space of x=0.140~0.265, y=0.570~0.720, and a stimulus value Y of 16≦Y, and a better system can display x=0.140~ 0.230, y=0.610~0.720, and the stimulus value Y is a color space in the range of 18≦Y. In addition, the film thickness of the cured film is coated with a photosensitive coloring resin composition, dried, and then exposed, and the polyfunctional monomer is cured, and then dried in a dust-free furnace at 230 ° C. The film thickness after baking for 30 minutes.

The chromaticity coordinates in the XYZ color system of JIS Z8701 which can be measured with a C-light source with a thickness of 2.8 μm or less and a single pixel are expressed as x=0.140 to 0.230, y=0.610 to 0.720, and A good blending ratio or combination of the color space in which the stimulation value Y is in the range of 18 ≦ Y is preferably the above-mentioned (Y1) as a yellow color material; and preferably a green color material containing CI color green 59 relative to the total amount of the color material. 10~70 quality The amount %, the blue color material is 5 to 50% by mass, and the yellow color material is 10 to 70% by mass; and the green color material containing CI color green 59 is preferably 15 to 60% by mass, blue color, relative to the total amount of the color material. The material is 10 to 40% by mass, and the yellow color material is 20 to 60% by mass.

Further, as a good blending ratio or combination of color spaces which can be expressed as x=0.180 to 0.265, y=0.570 to 0.710, and a stimulus value Y of 16≦Y, it is preferable to use the above (Y2) as a yellow color material; Preferably, the green color material containing CI color green 59 is 10 to 70% by mass, the blue color material is 5 to 50% by mass, and the yellow color material is 10 to 70% by mass with respect to the total amount of the color material; More preferably, the green color material containing CI pigment green 59 is 15 to 60% by mass, the blue color material is 10 to 40% by mass, and the yellow color material is 20 to 60% by mass.

<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. For example, an alkali-soluble resin or a polyfunctional group may be added to the color material dispersion liquid of the second invention of the present invention. The monomer, the photoinitiator, and other components as needed are obtained by mixing using a known mixing means. In the case of containing another color material different from PG59 as in the second embodiment or the third embodiment, the color material dispersion liquid of PG59 and the color material dispersion liquid of yellow color material are separately prepared by using the above dispersant. A color material dispersion liquid of other color materials as needed, a color material dispersion liquid containing PG59, a color material dispersion liquid containing yellow color material, a color material dispersion liquid of other color materials as needed, an alkali-soluble resin, and a polyfunctional function. The base monomer, the photoinitiator, and other components as needed are mixed by a known mixing means to obtain a photosensitive colored resin composition for a color filter.

II-3. Second color filter related to the present invention

A second color filter according to the present invention includes at least a transparent substrate and a coloring layer provided on the transparent substrate, wherein at least one of the colored layers has a second invention related to the present invention The colored filter is formed by curing the photosensitive colored resin composition to form a colored layer.

In the second color filter of the present invention, at least one of the colored layers may have a coloring layer formed by curing the photosensitive coloring resin composition for a color filter according to the second aspect of the present invention. A color filter excellent in high luminance and high contrast and excellent in color reproducibility.

In the second color filter according to the present invention, if the color filter layer formed by curing the photosensitive coloring resin composition according to the second aspect of the present invention is cured, the other configuration may be the same as the first one. Since the color filters of the invention are the same, the description is omitted here.

II-4, 5. Second liquid crystal display device and organic light emitting display device according to the present invention

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

A second organic light-emitting display device according to the present invention is characterized by comprising the second color filter of the present invention and an organic light-emitting body.

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

In the liquid crystal display device and the organic light-emitting display device according to the second aspect of the present invention, if the second color filter of the present invention is provided, the other configuration may be The liquid crystal display device and the organic light-emitting display device according to the first aspect of the present invention are the same as those described above, and thus the description thereof will be omitted.

(Example)

The following examples are given to illustrate the invention. The invention is not limited by the description.

The acid value of the block copolymer before the salt formation and the acid value of the salt block copolymer formed by the salt of the compound represented by the above general formula (2) are based on the method described in JIS K 0070. The method is obtained.

The amine valence of the block copolymer before salt formation and the amine valence of the salt block copolymer formed by salt formation of the compound represented by the above general formula (2) are based on the method described in JIS K 7237. The method is obtained.

The glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation is measured by the method described in JIS K 7121, using differential scanning calorimetry (DSC) (manufactured by SII Nano Technology Co., Ltd., Measured by EXSTAR DSC 7020).

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

Further, the glass transition temperatures (Tg) of the block copolymers A-1 and A-26 of the following synthesis examples and the block copolymers A-22 and A-24 of the comparative examples were determined by the following formula. As a result, the block copolymer A-1 was found to be 37 ° C (DSC measured value: 38 ° C), the block copolymer A-26 was 64 ° C (DSC measured value: 66 ° C), and the block copolymer A-22 was 0. °C (DSC measurement value: 2 ° C) and block copolymer A-24 were 20 ° C (DSC measurement value: 20 ° C), and the measurement was almost the same as the DSC measurement value.

1/Tg=Σ(Xi/Tgi)

Here, the block copolymerization system is such that i = n to n of the monomer components are copolymerized. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, the Σ is the sum of i=1 to n. Further, the value (Tgi) of the homopolymer glass transition temperature of each monomer was a value of Polymer Handbook (3rd Edition) (J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)). Specifically, the value (Tgi) of the homopolymer glass transition temperature of each monomer used in the examples and the comparative examples is as follows.

Methacrylic acid (MAA): 185 ° C

2-Hydroxyethyl methacrylate (HEMA): 55 ° C

2-ethylhexyl methacrylate (EHMA): -10 ° C

N-butyl methacrylate (BMA): 20 ° C

Benzyl methacrylate (BzMA): 54 ° C

Methyl methacrylate (MMA): 105 ° C

Cyclohexyl methacrylate (CHMA): 83 ° C

Dimethylaminoethyl methacrylate (DMMA): 18 ° C

Dimethylaminopropylmethacrylamide (DMAPMA): 96 ° C

Methoxy polyethylene glycol monomethacrylate (trade name: PME-100, manufactured by Nippon Oil Co., Ltd., BLEMMER-PME-100, ethylene oxide repeat number = 2): -26 ° C

Methoxy polyethylene glycol monomethacrylate (trade name: PME-200, manufactured by Nippon Oil Co., Ltd., BLEMMER-PME-200, ethylene oxide repeat number = 4): -59 ° C

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

Embodiment I Series: First Invention (Synthesis Example 1: Production of Block Copolymer A-1)

To a 500 mL round bottom four-necked flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 ° C, 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) as a monomer of B block, 18.6 parts by mass of 2-ethylhexyl methacrylate (EHMA), n-butyl methacrylate (BMA) 15.4 parts by mass, 9.5 parts by mass of benzyl methacrylate (BZMA), and 29.3 parts by mass of methyl methacrylate (MMA) were dropped using an addition funnel over 60 minutes. After 30 minutes, 27.0 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was dropped over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration, vacuum drying, and diluted with PGMEA to prepare a 30% by mass solid solution. 32.5 parts by mass of water was added, and the mixture was heated to 100 ° C for 7 hours, and the constituent unit derived from EEMA was deprotected to obtain a constituent unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, and purified by filtration and vacuum drying to obtain an A block containing a structural unit represented by the general formula (I) and a composition containing a carboxyl group-containing monomer. The block copolymerized polymer A-1 (acid value 1 mgKOH/g, Tg 38 ° C) having a solvophilic B block. The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography) to have a weight average molecular weight Mw of 7,600. Further, the amine value was 96 mgKOH/g.

(Synthesis Examples 2 to 3: Synthesis of Block Copolymers A-2 to A-3)

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

(Synthesis Example 4: Synthesis of Salt-Type Block Copolymer A-4)

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

In a 100 mL round pellet flask, 10.0 parts by mass of the block copolymer A-2 was dissolved in 41.93 parts by mass of PGMEA, and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) belonging to the compound represented by the above general formula (3) was added in an amount of 0.48 parts by mass. (The compound represented by the above general formula (3) is a DMMA unit 1 mole of the block copolymer A-2, which is 0.20 mol), and stirred at a reaction temperature of 30 ° C for 20 hours to obtain a solid content of 20% by mass of a salt. Type block copolymer A-4 solution. The acid value of the block copolymer after salt formation is the same as that of the block copolymer A-2, and the amine value after salt formation is specifically calculated as follows.

9 parts by mass of a salt-type block copolymer A-4 (solid matter after reprecipitation) and 1 g of a solution of 91 parts by mass of chloroform-D1 NMR were placed in an NMR sample tube, and a nuclear magnetic resonance apparatus (FTM, manufactured by JEOL Ltd.) was used. NMR, JNM-AL400), 13 C-NMR spectrum was measured under conditions of room temperature and cumulative number of times of 10,000 times. In the obtained spectral data, the ratio of the carbon atom peak adjacent to the nitrogen atom which is not formed by the salt, and the integral value of the carbon atom peak adjacent to the nitrogen atom formed by the salt, at the terminal nitrogen portion (amine group) The ratio of the number of amine groups formed by the salt to the total number of amine groups was calculated, and it was confirmed that it was different from the theoretical salt formation ratio (total phenylphosphonic acid was the terminal nitrogen of the DMMA of the block copolymer A-2). The part forms a salt).

The amine value (19 mg KOH/g) of 0.20 mole parts of the DMMA unit was subtracted from the amine value of 95 mgKOH/g before salt formation, and the amine value after salt formation was calculated to be 76 mgKOH/g. The Tg of the block copolymer before and after salt formation is shown in Table 1.

(Synthesis Examples 5 to 10: Synthesis of Salt-Type Block Copolymers A-5 to A-10)

In the same manner as in Synthesis Example 4 except that the salt-forming compound was changed to the compound and the amount shown in Table 1, a solution of the salt-type block copolymer A-5 to A-10 was obtained.

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

Further, in Table 1, the amount of one or more compounds selected from the group consisting of the compounds represented by the above general formulas (1) to (3) is constituted by the molar number of the above compound relative to the general formula (I). The nitrogen content of the unit (DMMA) is expressed by 1 mol.

(Synthesis Examples 11 to 12: Synthesis of Salt-Type Block Copolymers A-11 to A-12)

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

(Synthesis Example 13: Production of Block Copolymer A-13)

In a 500 mL round bottom four-necked flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, tetrahydrofuran was added via an addition funnel. 250 parts by mass of THF (THF) and 5.81 parts by mass of dimethyl ketene methyltrimethyldecyl acetal of the initiator were sufficiently substituted with nitrogen. 0.5 parts by mass of a catalyst of tetrabutylammonium o-chlorobenzoic acid in a 1 mol/L acetonitrile solution was injected using a syringe, and the B block monomer was HEMA 18.7 parts by mass and EHMA 12.8 mass using an addition funnel. A portion, BMA 13.7 parts by mass, BzMA 9.5 parts by mass, and MMA 19.5 parts by mass were dropped over 60 minutes. The reaction flask was cooled in an ice bath by keeping the temperature below 40 °C. After 1 hour, 25.8 parts by mass of DMMA belonging to the monomer for the A block was dropped over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to terminate the reaction. The obtained block copolymer THF solution is reprecipitated in hexane, and purified by filtration and vacuum drying to obtain an A block containing a structural unit represented by the general formula (I), and a B-containing solvophilic substance. Segment of the block copolymer A-13 (Tg 37 ° C). The block copolymer A-13 thus obtained was confirmed by GPC (gel permeation chromatography) to have a weight average molecular weight Mw of 7,320. Further, the amine value was 92 mgKOH/g.

(Synthesis Examples 14 to 17: Synthesis of Salt-Type Block Copolymers A-14 to A-17)

In Synthesis Example 4, except for the block copolymer A-13 of Synthesis Example 13 (block copolymer before the formation of the salt of the salt block copolymer A-14 to A-17 and the block copolymer A-13) The same as in the case of the salt-forming compound, which was changed to the compound and the amount shown in Table 1, except that the salt-forming compound was changed to the salt-type block copolymer A-14 to A-17. Solution.

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

(Synthesis Examples 18 to 34: Synthesis of Block Copolymers A-18 to A-34)

In the synthesis example 1, the block copolymers A-18 to A-34 used in the examples or the comparative examples were synthesized in the same manner as in the synthesis example 1 except that the amounts shown in Table 2 or Table 3 were changed. The acid value, Tg, and amine price 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)

In Synthesis Example 4, except that the block copolymer A-33 of Synthesis Example 33 (the block copolymer before the formation of the salt of the salt block copolymer A-35 to A-37 and the block copolymer A-33) was used. The same as in the case of the salt-forming compound, which was changed to the compound and the amount shown in Table 3, and the same as in Synthesis Example 4, the salt-type block copolymer A-35 to A-37 was obtained. Solution.

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

(Synthesis Examples 38 to 40: Synthesis of Block Copolymers A-38 to A-40)

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

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

300 parts by mass of PGMEA was placed in a polymerization tank, and after heating to 100 ° C in a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA) and MMA54 were used. In parts, 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 shifting agent (n-dodecylmercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction was continued at 100 ° C, and after 2 hours from the completion of the dropwise addition of the above-mentioned main chain-forming mixture, 0.1 part by mass of p-methoxyphenol as a polymerization inhibiting agent was added to stop the polymerization.

Next, 20 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound while blowing air, and the temperature was raised to 110 ° C, and 0.8 parts by mass of triethylamine was added thereto to carry out an addition reaction at 110 ° C. In an hour, an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value: 75 mgKOH/g, solid content: 40% by mass) was obtained.

Further, the above method for measuring the weight average molecular weight is carried out by using polystyrene as a standard material and measuring the weight average molecular weight by Shodex GPC system-21H (Shodex GPC system-21H) using THF as an eluent. Further, the method for measuring the acid value is measured in accordance with JIS K 0070.

(Example 1) (1) Manufacture of color material dispersion G-1

3.25 parts by mass of the block copolymer A-1 of Synthesis Example 1 as a dispersing agent, 11.7 parts by mass of CI Pigment Green 58 (PG58) as a color material, 1.3 parts by mass of CI Pigment Yellow 138 (PY138), and Synthesis Example 41 16.25 parts by mass of the alkali-soluble resin A solution, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle and shaken for 1 hour with a pigment shaker (made by Asada Iron Works Co., Ltd.). As a preliminary pulverization, zirconia beads having a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and the mixture was dispersed in a pigment shaker for 4 hours in the same manner to be officially pulverized to obtain a color material dispersion G. -1.

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

11.40 parts by mass of the color material dispersion liquid G-1 obtained in the above (1), 0.64 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 41, and a polyfunctional monomer (trade name: ARONIX M-403, East Asia Synthetic Co., Ltd.) Company made) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2- Phytylpropan-1-one (photoinitiator: trade name IRGACURE 907, manufactured by BASF JAPAN Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (light initiator: trade name IRGACURE 369, manufactured by BASF JAPAN) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-, 1-(o-ethylindenyl) (photoinitiator: trade name: IRGACURE OXE02, manufactured by BASF JAPAN Co., Ltd.) 0.02 parts by mass, fluorine-based surfactant ( 0.07 parts by mass and 7.14 parts by mass of PGMEA, the product name MEGAFACE R-08MH, manufactured by DIC Co., Ltd., was used to obtain a photosensitive colored resin composition G-1 for a color filter.

(Examples 2 to 26) (1) Manufacture of color material dispersion G-2~G-26

In (1) of the first embodiment, except for the substituted block copolymer A-1, as shown in Tables 5 to 7, respectively, the solid content is the same as the mass of the block copolymer A-1. Block copolymers A-2 to A-3 of Synthesis Examples 2 to 3, salt type block copolymers A-4 to A-10 of Synthesis Examples 4 to 10, and block copolymers of Synthesis Examples 18 to 21 were used. A-18~A-21, block copolymers A-26~A-32 of Synthesis Examples 26-32, Block copolymers A-33~A-34 of Synthesis Examples 33-34, and Synthesis Examples 35-37 The salt type block copolymer A-35~A-37 solution is adjusted in a total amount of 100 parts by mass to adjust PGMEA The amount of the color material dispersions G-2 to G-26 was obtained in the same manner as in the above (1).

(2) Manufacture of photosensitive colored resin composition G-2 to G-26 for color filters

In (2) of the first embodiment, the color material dispersion liquid G-1 was used, and the color material dispersion liquids G-2 to G-26 were used, respectively, and the color was obtained in the same manner as in the second embodiment (2). The photosensitive coloring resin composition G-2 to G-26 was used for the filter.

(Example 35) (1) Manufacture of color material dispersion G-27

3.25 parts by mass of the block copolymer A-2 of Synthesis Example 2 as a dispersing agent, 13 parts by mass of CI Pigment Green 59 (PG59, manufactured by FASTOGEN GREEN C100 DIC Co., Ltd.) as a color material, and Synthesis Example 41 16.25 parts by mass of the alkali-soluble resin A solution, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle and shaken for 1 hour with a pigment shaker (made by Asada Iron Works Co., Ltd.). As a preliminary pulverization, zirconia beads having a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and the mixture was dispersed in a pigment shaker for 4 hours in the same manner to be officially pulverized to obtain a color material dispersion G. -27.

(2) Manufacture of photosensitive colored resin composition G-27 for color filters

In the second embodiment of the present invention, except for the color material dispersion liquid G-1, the color material dispersion liquid G-27 was used, and the same procedure as in the second embodiment (2) was carried out to obtain a color filter. Photosensitive colored resin composition G-27.

(Examples 36 to 38) (1) Manufacture of color material dispersion G-28~G-30

In (1) of Example 35, except for the substituted block copolymer A-2, respectively As shown in Table 8, the salt type block copolymer A-8 solution of Synthesis Example 8 and the block copolymerized product A of Synthesis Example 33 were used in the same manner as in the case of the same mass parts of the block copolymer A-2. 33 and the salt-type block copolymer A-35 solution of Synthesis Example 35, except that the amount of PGMEA was adjusted to 100 parts by mass in total, and the same procedure as in (1) of Example 35 was carried out to obtain a color material dispersion G-28. ~G-30.

(2) Manufacture of photosensitive colored resin composition G-28 to G-30 for color filters

(2) of Example 35, except that the color material dispersion liquid G-27 was used, and the color material dispersion liquids G-28 to G-30 were used, respectively, and the same procedure as in (2) of Example 35 was carried out. The color filter is a photosensitive colored resin composition G-28 to G-30.

(Example 39)

In (1) of Example 1, CI Pigment Green 59 (PG59, trade name: FASTOGEN GREEN C100 DIC Co., Ltd.) was used instead of CI Pigment Green 58 (PG58) as a color material, and was substituted as a dispersing agent. The block copolymer A-1 of Synthesis Example 1 was used in the same manner as in (1) of Example 1 except that the block copolymer A-2 of Synthesis Example 2 was used, and a color material dispersion liquid G-31 was obtained.

(2) Manufacture of photosensitive colored resin composition G-31 for color filter

In the second embodiment of the present invention, except for the color material dispersion liquid G-1, the color material dispersion liquid G-31 was used, and the color filter was obtained in the same manner as in the second embodiment (2). Photosensitive colored resin composition G-31.

(Examples 40 to 42) (1) Manufacture of color material dispersion G-32~G-34

In (1) of Example 39, except for the substituted block copolymer A-2, respectively As shown in Table 8, the salt type block copolymer A-8 solution of Synthesis Example 8 and the block copolymerized product A of Synthesis Example 33 were used in the same manner as in the case of the same mass parts of the block copolymer A-2. 33 and the salt-type block copolymer A-35 solution of Synthesis Example 35 were adjusted in the same manner as in (1) of Example 39 except that the amount of PGMEA was adjusted to 100 parts by mass in total, to obtain a color material dispersion G-32. ~G-34.

(2) Manufacture of photosensitive colored resin composition G-32~G-34 for color filters

In (2) of Example 39, except for the above-mentioned color material dispersion liquid G-32 to G-34, the color material dispersion liquid G-31 was used, and the color was obtained in the same manner as in (2) of Example 39, and color was obtained. The filter was made of a photosensitive colored resin composition G-32 to G-34.

(Comparative examples 1 to 14) (1) Manufacture of comparative color material dispersions G-1 to G14

In (1) of the first embodiment, except for the substituted block copolymer A-1, as shown in Tables 5 to 7, respectively, the solid content is the same as the mass of the block copolymer A-1. The block copolymers A-11 to A-13 of Synthesis Examples 11 to 13, the salt type block copolymers A-14 to A-17 of Synthesis Examples 14 to 17, and the block copolymerization of Synthesis Examples 22 to 25 were used. In addition to the PGMEA amount, the amount of the PGMEA is adjusted to 100 parts by mass in total, and the (1) of the first embodiment is the same as the one of the first embodiment. In the same manner, comparative color material dispersions G-1 to G-14 were obtained.

(2) Manufacture of photosensitive coloring resin composition G-1 to G-14 for comparison of color filters

(2) in the first embodiment, except that the above-mentioned comparative color material dispersions G-1 to G-11 are used as the substitute color material dispersion liquid G-1, the same as in the second embodiment (2). The photosensitive colored resin compositions G-1 to G-14 for comparative color filters were obtained.

(Example 27) (1) Manufacture of color material dispersion R-1

3.25 parts by mass of the block copolymer A-1 of Synthesis Example 1 as a dispersing agent, 6.5 parts by mass of CI Pigment Red 177 (PR177) as a pigment, and 6.5 parts by mass of CI Pigment Red 254 (PR254), and Synthesis Example 41 16.25 parts by mass of the alkali-soluble resin A solution, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle and shaken for 1 hour with a pigment shaker (made by Asada Iron Works Co., Ltd.). After pre-disintegration, the zirconia beads having a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and the mixture was dispersed for 4 hours by a pigment shaker in the same manner as an officially pulverized to obtain a color material dispersion R- 1.

(2) Manufacture of photosensitive colored resin composition R-1 for color filters

11.40 parts by mass of the color material dispersion R-1 obtained in the above (1), 0.64 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 41, and a polyfunctional monomer (trade name: ARONIX M-403, East Asia Synthetic Co., Ltd.) Company made) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2- Phytylpropan-1-one (photoinitiator: trade name IRGACURE 907, manufactured by BASF JAPAN Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (light initiator: trade name IRGACURE 369, manufactured by BASF JAPAN) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-, 1-(o-ethylindenyl) (photoinitiator: trade name: IRGACURE OXE02, manufactured by BASF JAPAN Co., Ltd.) 0.02 parts by mass, fluorine-based surfactant ( 0.07 parts by mass of MEGAFACE R-08MH, manufactured by DIC Co., Ltd., and 7.14 parts by mass of PGMEA, and a photosensitive colored resin composition R-1 for a color filter was obtained.

(Examples 28 to 30) (1) Manufacture of color material dispersion R-2~R-4

In (1) of the embodiment 27, in addition to the substituted block copolymer A-1, as shown in Table 9, the synthesis examples were respectively used in such a manner that the solid content became the same mass as the block copolymer A-1. The block copolymers A-27, A-3 and the salt type block copolymer A-4 solution of 27, 3 and 4 were adjusted to a total amount of PGMEA in a manner of 100 parts by mass in total, and the same as in Example 27 (1) In the same manner, the color material dispersions R-2 to R-4 were obtained.

(2) Manufacture of photosensitive colored resin composition R-2 to R-4 for color filters

(2) of Example 27, except that the color material dispersion liquid R-1 was used, and the color material dispersion liquids R-2 to R-4 were used, respectively, and the same procedure as in (2) of Example 27 was carried out. The photosensitive coloring resin composition R-2 to R-4 is used for the color filter.

(Comparative examples 15 to 18) (1) Manufacture of comparative color material dispersions R-1 to R-4

In (1) of Example 27, except that the substituted block copolymer A-1 was used, as shown in Table 9, the solid content was the same as that of the block copolymer A-1, and the synthesis was carried out separately. The block copolymers A-11, A-13, A-24, and A-25 of Examples 11, 13, 24, and 25 were adjusted to have a PGMEA amount in a total amount of 100 parts by mass, and the other examples were the same as those in Example 27 (1). The same procedure was carried out to obtain comparative color material dispersions R-1 to R-4.

(2) Manufacture of photosensitive colored resin composition R-1 to R-4 for comparison of color filters

In the second embodiment of the present invention, except for the above-mentioned comparative color material dispersion liquids R-1 to R-4, the same color material dispersion liquid R-1 was used, and the same procedure as in the second embodiment (2) was carried out. The photosensitive colored resin compositions R-1 to R-4 for comparative color filters were obtained.

(Example 31) (1) Manufacture of color material dispersion B-1

A-13.25 parts by mass of the block copolymer of Synthesis Example 1 as a dispersing agent, 10.4 parts by mass of CI Pigment Blue 15:6 (PB15:6) as a pigment, and 2.6 parts by mass of CI Pigment Violet 23 (PV23), Synthesis Example 41.25 parts by mass of the alkali-soluble resin A solution obtained, 41 parts by mass of PGMEA, and 6 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle and oscillated by a pigment shaker (made by Asada Iron Works Co., Ltd.). 1 hour was prepared as a preliminary pulverization, and then zirconia beads having a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and similarly dispersed by a pigment shaker for 4 hours to be officially pulverized to obtain a color material dispersion. Liquid B-1.

(2) Manufacture of photosensitive colored resin composition B-1 for color filters

8.59 parts by mass of the color material dispersion B-1 obtained in the above (1), 1.05 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 41, and a polyfunctional monomer (trade name: ARONIX M-403, East Asia Synthetic Co., Ltd.) Company made) 0.98 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (photoinitiator: trade name IRGACURE 907, manufactured by BASF JAPAN Co., Ltd.) 0.15 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE 369, manufactured by BASF JAPAN) 0.07 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-, 1-(o-ethylindenyl) (photoinitiator: trade name: IRGACURE OXE02, manufactured by BASF JAPAN Co., Ltd.) 0.03 parts by mass, fluorine-based surfactant ( The product name MEGAFACE R-08MH, manufactured by DIC Co., Ltd., was 0.07 parts by mass, and PGMEA was 9.06 parts by mass to obtain a photosensitive colored resin composition B-1 for a color filter.

(Examples 32 to 34) (1) Manufacture of color material dispersion B-2~B-4

In (1) of the example 31, in addition to the substituted block copolymer A-1, as shown in Table 10, the synthesis examples were respectively used in such a manner that the solid content became the same mass part as that of the block copolymer A-1. The block copolymers A-27, A-3 and the salt block copolymer A-4 solution of 27, 3 and 4 were adjusted to a total amount of PGMEA in a total amount of 100 parts by mass, and the other was in the same manner as in Example 31 (1). In the same manner, the color material dispersions B-2 to B-4 were obtained.

(2) Manufacture of photosensitive colored resin composition B-2 to B-4 for color filters

In (2) of Example 31, except that the color material dispersion liquid B-1 was used instead of the color material dispersion liquids B-2 to B-4, the same procedure as in (2) of Example 31 was carried out. Photosensitive coloring resin composition B-2 to B-4 for color filters.

(Comparative examples 19 to 22) (1) Manufacture of comparative color material dispersions B-1 to B-4

In (1) of the example 31, in addition to the substituted block copolymer A-1, as shown in Table 10, the synthesis examples were respectively used in such a manner that the solid content became the same mass part as that of the block copolymer A-1. The block copolymers A-11, A-13, A-24, and A-25 of 11, 13, 24, and 25 were adjusted to the amount of PGMEA in a total amount of 100 parts by mass, and the other (1) of Example 31 In the same manner, comparative color material dispersions B-1 to B-4 were obtained.

(2) Manufacture of photosensitive colored resin compositions B-1 to B-4 for comparison of color filters

In (2) of the embodiment 31, the same as the above-mentioned comparative color material dispersion liquids B-1 to B-4 except for the substitute color material dispersion liquid B-1, the same as in the second embodiment (2). In the row, photosensitive photosensitive resin compositions B-1 to B-4 for comparative color filters were obtained.

[Evaluation method] <Dispersibility evaluation of color material dispersion>

The viscosity of the color material dispersion obtained in the examples and the comparative examples was measured immediately after preparation and after storage at 25 ° C for 30 days, and the viscosity change rate was calculated from the viscosity before and after storage, and the viscosity stability was evaluated. The viscosity was measured using a vibrating viscometer to measure a viscosity of 25.0 ± 0.5 °C. The results are shown in Tables 5 to 10.

(Standard for dispersion stability evaluation)

A: The viscosity change rate before and after storage is less than 15%

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

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

D: The viscosity change rate before and after storage is 40% or more

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

In the evaluation result, the color material dispersion liquid of C is practically used. However, when the evaluation result is B, the color material dispersion liquid is more excellent, and when the evaluation result is A, the dispersion stability of the color material dispersion liquid is excellent.

<Optical performance evaluation, comparative evaluation>

The color filter of the color filter obtained in the examples and the comparative examples was used for a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm. After the applicator was applied, it was dried at 80 ° C for 3 minutes using a hot plate, thereby forming a coloring layer. Ultraviolet rays of 60 mJ/cm ² were irradiated to the colored layer using an ultrahigh pressure mercury lamp.

Next, the colored substrate was post-baked in a dust-free oven at 230 ° C for 30 minutes, and the contrast and color of the obtained colored substrate were measured using a kettle-making electrical comparison measuring device CT-1B and an Olympus microscopic spectroscopic measuring device OSP-SP200. Degree (x, y), luminance (Y). The results are combined and shown in Tables 5-10.

(Comparative evaluation benchmark)

A: Green is over 7000, Red is over 5000, and Blue is over 5000.

B: Green is 6300~7000, Red is 4300~5000, Blue is 4300~5000

C: Green is less than 6300, Red is less than 4300, Blue is less than 4300

Among them, Green of Examples 1 to 26 and Comparative Examples 1 to 11 which are respectively set to C light source are y=0.570, Green of Examples 35 to 38 is y=0.420, and Green of Examples 39 to 42 is y=0.480. In the examples 27 to 30 and the comparative examples 12 to 15, Red was a value of x=0.650, and Examples 31 to 34 and Comparative Examples 16 to 19 were values of y=0.107.

<Development residue evaluation>

The color filter of the color filter obtained in the examples and the comparative examples was used for a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm. After the applicator was applied, it was dried at 80 ° C for 3 minutes using a hot plate, thereby forming a coloring layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer was visually observed, and then thoroughly wiped with a lens cleaning cloth (manufactured by Toray Industries, Inc., trade name: TORAYSEE MK cleaning cloth) containing ethanol, and the lens was visually observed. The degree of coloring of the cleaning cloth. The results are shown in Tables 5 to 10.

(Development residue evaluation standard)

A: The development residue was not visually confirmed, and the lens cleaning cloth was completely colorless.

B: The development residue was not visually confirmed, and it was confirmed that the lens cleaning cloth was slightly colored.

C: A slight development residue was visually confirmed, and it was confirmed that the lens cleaning cloth was slightly colored.

D: A slight development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.

E: Visually confirm the development residue and confirm the color of the lens cleaning cloth.

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

<Development and adhesion evaluation>

The color filter of the color filter obtained in the examples and the comparative examples was used for a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm. After the applicator was applied, it was dried at 80 ° C for 3 minutes using a hot plate, thereby forming a coloring layer having a thickness of 2.5 μm. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask having a mask opening width of 2 to 80 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The developed substrate was observed with an optical microscope to observe the presence or absence of a colored layer with respect to the opening line width of the mask. The results are shown in Tables 5 to 10.

(Development adhesion evaluation standard)

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

B: Coloring was observed in a portion of the mask opening line width of 10 μm or more and less than 20 μm. Floor

C: a colored layer was observed in a portion of the mask opening line width of 20 μm or more and less than 50 μm.

D: a colored layer was observed in a portion of the mask having an opening line width of 50 μm or more and less than 80 μm.

E: no colored layer was observed in the portion of the mask opening line width of 80 μm or less.

When the evaluation result is C, the photosensitive colored resin composition for a color filter can be used practically. However, if the evaluation result is B, the photosensitive colored resin composition for a color filter is suitable for a higher definition. When the evaluation result is A, the photosensitive coloring resin composition for a color filter can be applied to a case where it is more highly refined.

<Evaluation of solvent resolubility>

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

(Solvent resolubility evaluation standard)

A: The dry coating film is completely dissolved

B: a sheet of a dried coating film is produced in a solvent, and the sheet is slightly dissolved

C: a thin film of a dried coating film is produced in a solvent, and the solution is colored.

D: a thin film of a dried coating film is produced in a solvent, and the solution is not colored.

E: no thin film of the dried coating film was produced in the solvent, and the solution was not colored.

When the evaluation criteria of the development residue are A, B or C, it is evaluated that the solvent resolubility is good, and it can be used practically without problems.

[Results integration]

From the results of Tables 1 to 10, it is apparent that the A block having the structural unit represented by the above general formula (I) and the constituent unit containing the carboxyl group-containing monomer and having solvophilic properties are used. a block copolymer of the block; and at least a part of the nitrogen moiety of the constituent unit represented by the general formula (I) of the block copolymer, and selected from the following general formulas (1) to (3) One or more compounds of the compound group form at least one of the salt block copolymers of the salt, and the acid value of the dispersant is 1 to 18 mgKOH/g, and the glass transition temperature of the dispersant is 30° C. or higher. The color material dispersion liquid of Examples 1 to 42 of the dispersing agent was excellent in dispersibility of the color material. Further, the photosensitive coloring resin composition for color filters of Examples 1 to 42 prepared by using the color material dispersion liquids of Examples 1 to 42 was excellent in dispersion stability of color materials, suppressed development residue, and developed. Excellent adhesion and solvent resolubility.

Among them, Examples 4 to 10 and 24 to 26, 30, 34, 36, 38, 40 and 42 of the above-described salt type block copolymer were used, and the color material dispersibility was particularly excellent, and the obtained colored layer was superior in comparison.

On the other hand, although the glass transition temperature of the dispersant is 30 ° C or higher, the comparative examples 1, 2, 12 to 14, 15 and 19 having an acid value higher than the specific value of the present invention are poor in developing adhesion and higher in acid value. In Comparative Examples 2 and 12 to 14, the solvent resolubility also deteriorated. On the other hand, although the glass transition temperature of the dispersant was 30 ° C or more, the comparative examples 3 to 7, 16 and 20 in which the acid value was lower than the specific value of the present case were inferior in the evaluation of the development residue. Although the acid value of the dispersing agent was a specific value of the present case, the glass transition temperature of the dispersing agent was lower than the specific values of the present examples, Comparative Examples 8 to 10, 17 and 21, and the development adhesiveness was poor. Further, Comparative Examples 11, 18 and 22 in which the glass transition temperature of the dispersing agent was 23 ° C and the acid value was higher than the specific value of the present case were development adhesiveness. difference.

Embodiment II Series: Second Embodiment of the Invention (Synthesis Example II-1: Modulation of Dispersant a)

The 500-ml four-necked flask was dried under reduced pressure, and then subjected to Ar (argon) replacement.

While blowing Ar gas, 100 g of dehydrated THF, 2.0 g of methyltrimethyldecyl dimethyl ketene acetal, and 0.15 ml of a 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoic acid (TBACB) were added. 0.2g. Methyl methacrylate (MMA) 36.7 g was dropped over 45 minutes using a dropping funnel. Since the reaction was heated, the temperature was kept below 40 ° C by an ice bath. After 1 hour, 13.3 g of dimethylaminoethyl methacrylate (DMMA) was dropped over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to give a block copolymer II-A1. The mass average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 6,000, and the amine value was 95 mgKOH/g.

In a 100 mL round pellet flask, 29.35 parts by mass of the block copolymer A-1 was dissolved in 29.35 parts by mass of PGMEA, and phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry Co., Ltd.) of the compound represented by the above general formula (3) was added. The mass fraction (relative to the above-mentioned general formula (3) is a DMMA unit of the block copolymer 1 of 1 mol, 0.20 mol), and stirred at a reaction temperature of 30 ° C for 20 hours to obtain a salt type block copolymer II. -A1 (dispersant a). The amine value after salt formation is specifically calculated as follows.

9 parts by mass of a salt-type block copolymer II-A1 (solid substance after reprecipitation) and 1 g of a solution of 91 parts by mass of chloroform-D1 NMR were placed in an NMR sample tube, and a nuclear magnetic resonance apparatus (FTM, manufactured by JEOL Ltd.) was used. NMR, JNM-AL400), 13 C-NMR spectrum was measured under conditions of room temperature and cumulative number of times of 10,000 times. In the obtained spectral data, at the end The nitrogen moiety (amine group) at the end is calculated from the ratio of the carbon atom peak adjacent to the nitrogen atom in which the salt is not formed and the integral value of the carbon atom peak adjacent to the nitrogen atom formed by the salt. The ratio of the base number to the total number of amine groups was confirmed to be different from the theoretical salt formation ratio (the two acidic groups of the total phenylphosphonic acid form a salt with the nitrogen moiety at the terminal of the DMMA of the block copolymer II-A1).

The amine value (38 mg KOH/g) of 0.40 mole parts of the DMMA unit was subtracted from the amine value of 95 mgKOH/g before salt formation, and the amine value after salt formation was calculated to be 57 mgKOH/g. The Tg of the block copolymer before and after salt formation is shown in Table 11.

(Synthesis Example II-2: Production of Dispersant b)

The salt block copolymerized polymer A-8 of Synthesis Example 8 of Example I was used in the same manner to obtain a solution of the salt block copolymer II-A2 (dispersant b). The acid value of the block copolymer after salt formation is the same as that of the salt-forming front block copolymer II-A2, and the amine value after salt formation is specifically calculated in the same manner as in Synthesis Example II-1.

(Synthesis Example II-3: Preparation of Dispersant c)

The 500-ml four-necked flask was dried under reduced pressure, and then subjected to Ar (argon) replacement.

While blowing Ar gas, 100 g of dehydrated THF, 2.0 g of methyltrimethyldecyl dimethyl ketene acetal, and 0.15 ml of a 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoic acid (TBACB) were added. 0.2g. Using a dropping funnel, 33 g of methyl methacrylate was dropped over 45 minutes. Since the reaction was heated, the temperature was kept below 40 ° C by an ice bath. After 1 hour, 17 g of dimethylaminoethyl methacrylate was dropped over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to give the block copolymer II-A3. The mass average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 6,000, and the amine value was 120 mgKOH/g.

In a 100 mL round pellet flask, 24.15 parts by mass of PGMEA was dissolved in 24.15 parts by mass of block copolymer II-A3, and phenylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) of the compound represented by the above general formula (3) was added. The compound (the DMMA unit 1 mol of the block copolymer II-A3 is 0.20 mol), and the mixture is stirred at a reaction temperature of 30 ° C for 20 hours to obtain a solid content of 20% by mass. Salt-type block copolymer II-A3 (dispersant c) solution. The amine value after salt formation was specifically calculated in the same manner as in Synthesis Example II-1.

(Synthesis Example II-4: Synthesis of Dispersant d)

In Synthesis Example II-2, except that the content shown in Table 11 was changed, the same procedure as in Synthesis Example II-2 was carried out, and a salt was formed to form a front block copolymer II-A4 and a salt block copolymer (dispersant). d) solution. In Synthesis Example II-4, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. The acid value, Tg, and amine value of the salt-forming block copolymer, the salt-type block copolymer, and the amine salt are shown in Table 11.

(Synthesis Example II-5: Synthesis of Dispersant e)

The block copolymer II-A2 (acid value: 8 mgKOH/g, Tg38 °C) was formed in the same manner as the salt of Synthesis Example II-2, and the block copolymer II-A5 (dispersant e) was synthesized.

(Synthesis Example II-6 to II-7: Synthesis of Dispersant f and Dispersant g)

In the synthesis example II-5, except that the monomer and the content shown in Table 11 were changed, the same procedure as in the synthesis example II-5 was carried out to synthesize the block copolymer II-A6 (dispersant f) and Block copolymer II-A7 (dispersant g). The acid value, Tg, and amine price of the obtained block copolymer are shown in Table 11.

(Synthesis Example II-8: Production of Dispersant h)

In Synthesis Example II-2, except that the monomer and the content shown in Table 11 were changed, the same procedure as in Synthesis Example II-2 was carried out, and a salt was formed to form a front block copolymer II-A8. The salt was used to form the front block copolymer II-A8, and the salt-forming compound was changed to the amount shown in Table 11, and the same procedure as in Synthesis Example II-2 was carried out to obtain a salt type block copolymer II-A8 (dispersant h). ) solution. The acid value, Tg, and amine value of the salt-forming block copolymer, the salt-type block copolymer, and the amine salt are shown in Table 11.

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

In a polymerization tank in which 150 parts by mass of PGMEA was placed, 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 dropped at 100 ° C for 3 hours under a nitrogen stream. After completion of the dropwise addition, the mixture was further heated at 100 ° C for 3 hours to obtain a polymer solution. The polymer solution had a weight average molecular weight of 7,000.

Next, 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 ° C for 10 hours to carry out carboxylic acid of the main chain methacrylic acid. The reaction of a group with an epoxy group of glycidyl methacrylate. In the reaction, air blowing was carried out in the reaction solution in order to prevent polymerization of glycidyl methacrylate. Still, the reaction was followed by measuring the acid value of the solution. The obtained alkali-soluble resin A solution is a resin obtained by copolymerization of BzMA with MMA and MAA, and a side chain of an ethylenic double bond introduced into the main chain using GMA, which is a solid content of 40% by mass and an acid value of 74 mgKOH/ g, weight average molecular weight of 12,000.

The abbreviations in the table are as follows.

PME-200: methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by Nippon Oil Co., Ltd., BLEMMER-PME-200, ethylene oxide repeat number = 4)

DMAPMA: dimethylaminopropyl methacrylamide

(Example II-1) (1) Manufacture of color material dispersion II-G1

6.18 parts by mass of a dispersing agent a solution of Synthesis Example II-1 as a dispersing agent, and 13.00 parts by mass of CI Pigment Green 59 (PG59, trade name: FASTOGEN GREEN C100 DIC Co., Ltd.) as a color material, and Synthesis Example 9. 14.63 parts by mass of the alkali-soluble resin A solution, 66.19 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle and shaken for 1 hour with a pigment shaker (made by Asada Iron Works Co., Ltd.). Prepared to be pulverized, and then oxidized zirconium beads having a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and similarly dispersed by a pigment shaker for 4 hours to be officially pulverized to obtain a color material dispersion II- G1.

(2) Manufacture of photosensitive colored resin composition II-G1 for color filters

11.40 parts by mass of the color material dispersion liquid II-G1 obtained in the above (1), 0.64 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example II-9, and a polyfunctional monomer (trade name: ARONIX M-403, East Asia Synthesis ( Co., Ltd.) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2- Orolinylpropan-1-one (photoinitiator: trade name: IRGACURE 907, manufactured by BASF Co., Ltd.), 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (light initiator: trade name IRGACURE 369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-, 1-(o-ethylindenyl) (photoinitiator: trade name: ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (product) 0.07 parts by mass of MEGAFACE F559, manufactured by DIC Co., Ltd., and 7.14 parts by mass of PGMEA, and a photosensitive colored resin composition II-G1 for a color filter was obtained.

(3) Formation of colored layer

The photosensitive colored resin composition II-G1 obtained in the above (2) was applied to a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm, respectively, using a spin coater. After coating, it was dried at 80 ° C for 3 minutes using a hot plate, irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp, and then post-baked in a dust-free oven at 230 ° C for 30 minutes, and became y=0.4 according to the C light source. The film thickness is adjusted by the chromaticity of x=0.2 to form the color layer II-G1.

(Examples II-2 to II-10, Comparative Example II-C1 to II-C4) (1) Manufacture of color material dispersions II-G2~II-G10, II-CG1~II-CG4

In (1) of Example II-1, in addition to the dispersant a solution, as shown in Table 12, the type and amount of the dispersant were changed so that the solid content became the same mass, and the comparative example was changed. The color material dispersions II-G2 to II-G10 and II-CG1 to II- were obtained in the same manner as in (1) of Example II-1 except that the amount of PGMEA was adjusted to 100 parts by mass in total. CG4.

(2) Manufacture of photosensitive colored resin composition II-G2~II-G10, II-CG1~II-CG4 for color filters

In Examples II-2 to II-10, and Comparative Examples II-C1 to II-C4, in place of the color material dispersion liquid II-G1 in (2) of Example II-1, the above-described color material dispersion was used, respectively. liquid Other than II-G2 to II-G10 and II-CG1 to II-CG4, the same procedure as in (2) of Example II-1 was carried out, and a photosensitive colored resin composition for color filters II-G2 to II-G10 was obtained. , II-CG1~II-CG4.

(3) Formation of colored layer

In (3) of the embodiment II-1, in addition to the photosensitive coloring resin composition II-G1, the photosensitive colored resin compositions II-G2 to II-G10 and II-CG1 to II-CG4 are used, respectively. The same procedure as in (3) of Example II-1 was carried out to obtain colored layers II-G2 to II-G10 and II-CG1 to II-CG4.

(Examples II-11 to II-14) (1) Manufacture of photosensitive colored resin composition II-G11~II-G14 for color filters

In the examples II-11 to II-14, in place of the color material dispersion liquid II-G1 in the second embodiment (II), the color material dispersion liquid II-G2 was used, and the photoinitiator was further changed. The photosensitive colored resin composition II-G11~II-G14 for color filters was obtained in the same manner as (2) of Example II-1 except the one shown in Table 12.

In Example II-13, in addition to the ethyl ketone in the substitution of (II) of Example II-1, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 0.02 parts by mass of 3-yl]-, 1-(o-ethenylhydrazine), changed to 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (photoinitiator: trade name IRGACURE 907, manufactured by BASF, IRG907) 0.10 parts by mass and 2-benzyl-2-dimethylamino-1-(4- In the same manner as (2) of Example II-1 except that the morphyl phenyl)-butanone-1 (photoinitiator: trade name: IRGACURE 369, manufactured by BASF, IRG369) was 0.05 parts by mass, the color filter was obtained. Photosensitive colored resin composition II-G13.

(3) Formation of colored layer

In (3) of the embodiment II-1, except for the photosensitive coloring resin composition II-G1, the photosensitive coloring resin composition II-G11 to II-G14 is used, respectively, and the other is the same as the example II-1. (3) In the same manner, colored layers II-G11 to II-G14 were obtained.

(Examples II-15, Comparative Examples II-C5)

In Example II-15, in (3) of Example II-1, except that the film thickness was adjusted so as to have a chromaticity of y=0.50 under the C light source to form a coloring layer, the same as Example II-1. (3) is also performed to form the colored layer II-G15.

Further, in Comparative Example II-C5, in (3) of Example II-1, except that the photosensitive colored resin composition II-G1 was replaced, the photosensitive colored resin composition II obtained in Comparative Example II-C2 was used. CG2 was formed in the same manner as (3) of Example II-1 except that the film thickness was adjusted so as to have a chromaticity of y=0.50 under the C light source, and the coloring layer II-CG5 was formed.

Here, the abbreviations in the table are as follows.

G58: C.I. Pigment Green 58 (trade name: FASTOGEN GREEN A110, manufactured by DIC Corporation)

G7: C.I. Pigment Green 7 (trade name: CHROMOFINE GREEN 6428EC, manufactured by Daisei Seiki Chemical Co., Ltd.)

Byk-2000: Disperbyk-2000 (manufactured by BYK Chemie, a polymer having a structural unit represented by the general formula (I), and the compound represented by the general formula (2) is a salt-forming block-type block copolymer, a solid portion 40% by mass)

N21116: Disperbyk-LPN21116 (manufactured by BYK Chemie, a polymer having a structural unit represented by the general formula (I), and the compound represented by the general formula (2) is a salt-forming salt block copolymer, and the solid content is 40 mass. %)

Byk-161: Disperbyk-161 (manufactured by BYK Chemie, urethane dispersant, solid content 30% by mass)

PB822: Ajisper PB822 (Ajinomoto FINE TECHNO (share), polyester dispersant, solid content 30% by mass)

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

TR-PBG-304: oxime ester photoinitiator (manufactured by Changzhou Power Electronic New Material Co., Ltd.)

OXE03: oxime ester photoinitiator (IRGACURE OXE-03, manufactured by BASF)

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

[Evaluation method] <Dispersibility evaluation of color material dispersion>

The viscosity of the color material dispersion obtained in the examples and the comparative examples was measured immediately after preparation and after storage at 25 ° C for 30 days, and the viscosity change rate was calculated from the viscosity before and after storage, and the viscosity stability was evaluated. The viscosity was measured using a vibrating viscometer to measure a viscosity of 25.0 ± 0.5 °C. The results are shown in Table 12.

(Standard for dispersion stability evaluation)

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

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

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

D: The viscosity change rate before and after storage is 25% or more

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

In the evaluation result, the color material dispersion liquid of C is practically used. However, if the evaluation result is B, the color material dispersion liquid is more excellent, and if the evaluation result is A, the dispersion stability of the color material dispersion liquid is excellent.

<Optical performance evaluation, comparative evaluation>

The contrast and chromaticity (x, y) and luminance (Y) of the colored layers obtained in the examples and the comparative examples were measured using a pot-and-bell electric comparison measuring device CT-1B and an Olympus microscopic spectrometry apparatus OSP-SP200.

Further, in Comparative Example 1 in which PG58 was used as the pigment, the chromaticity of y=0.4 and x=0.2 under the C light source was not achieved.

The results are combined and shown in Table 12.

(Color reproduction domain evaluation standard) ‧C value under y=0.4~0.5

A: x = 0.21 is not full

B: x = 0.21~0.23

C:x=more than 0.23

(brightness evaluation standard) ‧C value under y=0.4, x=0.2

A: More than 50.0

B: 47.5~50.0

C: less than 47.5

‧C value under y=0.5

A: More than 30.0

B: 30.0~25.0

C: less than 25.0

(Comparative evaluation benchmark) ‧C value under y=0.4, x=0.2

A: More than 15,000

B: 13500~15000

C: less than 13500

‧C value under y=0.5

A: More than 3,500

B: 2500~3500

C: less than 2500

<Evaluation of solvent resolubility>

The front end of the glass substrate having a width of 0.5 cm and a length of 10 cm is immersed in the embodiment and the ratio The photosensitive coloring resin composition for a color filter obtained in the comparative example was applied to the 1 cm long portion of the glass substrate. The glass substrate which was pulled up was placed in a constant temperature and humidity machine so that the glass surface was horizontal, and dried at a temperature of 23 ° C and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film adhered was immersed in PGMEA for 15 seconds. The re-dissolved state of the dried coating film at this time was visually discriminated and evaluated. The results are combined and shown in Table 12.

(Solvent resolubility evaluation standard)

A: The dry coating film is completely dissolved

B: a thin film of a dried coating film is produced in a solvent, and the solution is colored.

C: no thin film of the dried coating film was produced in the solvent, and the solution was not colored.

When the above evaluation criteria are A or B, it can be used practically, and if the evaluation result is A, the effect is more excellent.

<Development residue evaluation>

The color filter of the color filter obtained in the examples and the comparative examples was used for a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm. After the applicator was applied, it was dried at 60 ° C for 3 minutes using a hot plate, thereby forming a coloring layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer was visually observed, and then thoroughly wiped with a lens cleaning cloth (manufactured by Toray Industries, Inc., trade name: TORAYSEE MK cleaning cloth) containing ethanol, and the lens was visually observed. The degree of coloring of the cleaning cloth. The results are shown in Table 12.

(Development residue evaluation standard)

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

B: The development residue was not visually observed, and it was confirmed that the lens cleaning cloth was slightly colored.

C: A slight development residue was visually confirmed, and it was confirmed that the lens cleaning cloth was slightly colored.

D: A slight development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.

E: The development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.

If it is the above-mentioned evaluation criteria A, B or C, it can be used practically, and if the evaluation result is B and further A, the effect is further excellent.

<Development and adhesion evaluation>

The color filter of the color filter obtained in the examples and the comparative examples was used for a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm. After the applicator was applied, it was dried at 60 ° C for 3 minutes using a hot plate, thereby forming a coloring layer having a thickness of 2.5 μm. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask having a mask opening width of 2 to 80 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The developed substrate was observed with an optical microscope to observe the presence or absence of a colored layer with respect to the opening line width of the mask. The results are shown in Table 12.

(Development adhesion evaluation standard)

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

B: A colored layer was observed in a portion having a mask opening line width of 10 μm or more and less than 20 μm.

C: A colored layer was observed in a portion having a mask opening line width of 20 μm or more and less than 50 μm.

D: A colored layer was observed in a portion having a mask opening line width of 50 μm or more and less than 80 μm.

E: No colored layer was observed in a portion of the mask opening line width of 80 μm or less.

When the evaluation criteria are A, B or C, it is practical. However, if the evaluation result is B or even A, the photosensitive colored resin composition for a color filter is suitable for use in a higher definition.

<Development resistance evaluation>

The color filter of the color filter obtained in the examples and the comparative examples was coated on a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm, and coated with a spin coater. After the cloth was cloth-dried by heating at 80 ° C for 3 minutes using a hot plate, ultraviolet rays of 40 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp. The film thickness at this time was measured as T1 (μm). Thereafter, shower development was carried out using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution. The film thickness after development was measured as T2 (μm). Calculate T2/T1×100 (%). The results are shown in Table 12.

(Development resistance evaluation standard)

A: 95% or more

B: 90% or more and less than 95%

C: less than 90%

If the evaluation result is B, it is practical, but if the evaluation criterion is A, the effect is more excellent.

<Water Infiltration Evaluation>

The color filter obtained by each of the examples and the comparative examples was formed into a photosensitive colored resin composition on a glass substrate ("NA35" manufactured by NH TECHNO GLASS Co., Ltd.), and then baked by a spin coater. The film thickness of the color layer having a thickness of 1.6 μm was applied, and then dried at 60° C. for 3 minutes using a hot plate, and ultraviolet rays of 60 mJ/cm ^{2 were} entirely irradiated through an ultrahigh pressure mercury lamp through a photomask to form a glass substrate. Colored layer. Next, using 0.05 wt% of potassium hydroxide (KOH) as a developing solution, the solution was subjected to rotary development, and the solution was liquid-contacted with the developing solution for 60 seconds, and then washed with pure water to carry out development treatment, and the washed substrate was rotated for 10 seconds to be centrifuged. Immediately after the water was removed, the contact angle of the pure water was measured as described below, and the water bleeding was evaluated.

The contact angle of pure water was measured on the surface of the colored layer immediately after the water was removed by centrifugation, and a droplet of 1.0 μL of pure water was dropped, and the static contact angle after the dropping for 10 seconds was measured by the θ/2 method. The measurement apparatus was measured using a contact angle meter DM500 manufactured by Kyowa Interface Science Co., Ltd.

(evaluation benchmark)

A: The contact angle is 80 degrees or more

B: The contact angle is 65 degrees or more and less than 80 degrees.

C: contact angle of 50 degrees or more and less than 65 degrees

D: The contact angle is less than 50 degrees

If the water percolation evaluation standard is A or B, it is practical; but if the evaluation result is A, the effect is more excellent.

[Results integration]

It can be clearly seen from the results of Table 12 that C.I. Pigment Green 59 will belong to the general The color material dispersion liquids of Examples II-1 to II-10 of the polymer composition of the constituent unit represented by the formula (I) had good viscosity stability. On the other hand, in the color material dispersion liquid of Comparative Example II-C3 to II-C4 in which C.I. Pigment Green 59 was combined with a urethane dispersant or a polyester dispersant, the viscosity stability was remarkably deteriorated. Further, in the color material dispersion liquid of Comparative Example II-C2 in which C.I. Pigment Green 7 was combined with a dispersant having a polymer having a structural unit represented by the general formula (I), the viscosity stability was remarkably deteriorated.

The photosensitive colored resin composition for color filters of Examples II-1 to II-15 which are a dispersant of a polymer having a structural unit represented by the general formula (I) in combination with CI Pigment Green 59 is clearly attached to When y=0.40, the area of x=0.20 can be displayed, or when y=0.50, the blueish green of the area of x=0.16 can be displayed, and the luminance is high. Further, in the coloring green 59, a photosensitive coloring resin composition for color filters of Examples II-1 to II-15 which is a dispersing agent of a polymer having a structural unit represented by the general formula (I) is used. The color material has good dispersion stability, excellent contrast, excellent solvent resolubility, and further suppression of development residue.

Wherein, as a dispersing agent, it is a block copolymer having an A block comprising the structural unit represented by the above general formula (I) and a B block having a solvophilic component derived from a constituent unit of the carboxyl group-containing monomer; a salt type block copolymer which forms a salt with at least a part of a nitrogen portion of the constituent unit represented by the general formula (I); and the dispersant has an acid value of 1 mgKOH/g or more and 18 mgKOH/g or less. In Examples II-2, 4, 5, 8, and 11 to 14 in which the glass transition temperature was 30 ° C or more, the development residue was particularly suppressed and the development adhesiveness was excellent.

On the other hand, as shown in Comparative Example II-C1, when C.I. Pigment Green 58 was used, when y=0.4, the region of x=0.2 could not be displayed. Further, as shown in Comparative Example II-C2, when C.I. Pigment Green 7 is used, when y=0.4, a region of x=0.2 can be displayed, but Low brightness. As shown in Comparative Examples II to C5, when C.I. Pigment Green 7 was used, when y=0.50, the region of x=0.16 was displayed, but the luminance was low. Further, although not shown in the table, by C.I. Pigment Green 58, when y = 0.50, the region of x = 0.16 cannot be displayed.

Further, as shown in Comparative Example II-C2, when CI Pigment Green 7 is used, even if a dispersant belonging to a polymer having a structural unit represented by the general formula (I) is combined, the dispersibility is not good, so the contrast is low. Resolubility and residue are also deteriorated.

On the other hand, a photosensitive colored resin composition for a color filter of Comparative Example II-C3 to II-C4 in which a urethane dispersant or a polyester-based dispersant is combined with CI Pigment Green 59 Due to the deterioration of dispersion. Therefore, compared with the examples, the luminance is lowered, and the contrast is low, and the resolubility and residue are also deteriorated.

Further, in the examples, in the examples in which the oxime ester-based photoinitiator was used as the photoinitiator, it was apparent that the development resistance and the effect of suppressing water bleeding were high.

Embodiment III Series: Second Embodiment of the Second Embodiment of the Invention

In the Example III series, the dispersants a to h solutions were obtained in the same manner as in the synthesis examples II-1 to II-8 of the Example II series. Further, the alkali-soluble resin A solution was also obtained in the same manner as in Synthesis Example II-9 of the Example II series.

(Example III-1) (1) Manufacture of color material dispersion III-G1

6.22 parts by mass of a dispersant a solution as a dispersing agent, CI Pigment Green 59 (PG59, manufactured by FASTOGEN GREEN C100 DIC Co., Ltd.) as a color material, 5.33 parts by mass, and CI Pigment Yellow 138 (PY138, trade name: CHROMOFINE) YELLOW 6206EC, manufactured by Dairi Seiki Co., Ltd.) 7.67 parts by mass, alkali 14.59 parts by mass of the soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle, and shaken by a pigment shaker (made by Asada Iron Works Co., Ltd.) for 1 hour. After disintegrating, zirconia beads having a particle diameter of 2.0 mm were taken out, and 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and similarly dispersed by a pigment shaker for 4 hours to be officially pulverized to obtain a color material dispersion III-G1. .

(2) Manufacture of photosensitive colored resin composition III-G1 for color filters

11.40 parts by mass of the color material dispersion liquid III-G1 obtained in the above (1), 0.64 parts by mass of the alkali-soluble resin A solution, and 0.60 mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd.) , 2-methyl-1-(4-methylthiophenyl)-2- Orolinylpropan-1-one (photoinitiator: trade name: IRGACURE 907, manufactured by BASF Co., Ltd.), 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (light initiator: trade name IRGACURE 369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-, 1-(o-ethylindenyl) (photoinitiator: trade name: ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (product) 0.07 parts by mass of MEGAFACE F559, manufactured by DIC Co., Ltd., and 7.14 parts by mass of PGMEA, and a photosensitive colored resin composition III-G1 for a color filter was obtained.

(3) Formation of colored layer

The photosensitive colored resin composition III-G1 obtained in the above (2) was applied to a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm, respectively, using a spin coater. After coating, it was dried at 80 ° C for 3 minutes using a hot plate, irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp, and post-baked for 30 minutes in a dust-free oven at 230 ° C, and became y = 0.570 under a C light source. The film thickness was adjusted by the chromaticity of x=0.260 to form the color layer III-G1.

(Examples III-2 to III-10, Comparative Examples III-C1 to III-C5) (1) Manufacture of color material dispersions III-G2~III-G10, III-CG1~III-CG5

In (1) of Example III-1, in addition to the dispersant a solution, as shown in Table 13, the type and amount of the dispersant were changed so that the solid content became the same mass, Comparative Example III-C1 In the same manner as (1) of Example III-1, the color material dispersion liquid III-G2 to III-G10 was obtained, except that the PGMEA amount was adjusted in a total amount of 100 parts by mass. III-CG1~III-CG5.

(2) Manufacture of photosensitive colored resin composition III-G2~III-G10, III-CG1~III-CG5 for color filters

In the examples III-2 to III-10 and the comparative examples III-C1 to III-C5, in addition to the color material dispersion liquid III-G1 in the substitution of the second embodiment (III), the above color materials were used. In the dispersions III-G2 to III-G10 and III-CG1 to III-CG5, in order to adjust the film thickness to 2.35 μm, the amount of the alkali-soluble resin was adjusted so that the P/V ratios were the values shown in Table 13, respectively. In the same manner as (2) of Example III-1, photosensitive coloring resin compositions III-G2 to III-G10 and III-CG1 to III-CG5 for color filters were obtained.

(3) Formation of colored layer

In the third embodiment of the present invention, except for the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G2 to III-G10 and III-CG1 to III-CG5 are used. The same procedure as in (3) of Example III-1 was carried out to obtain colored layers III-G2 to III-G10 and III-CG1 to III-CG5.

(Examples III-11~III-14, III-33) (1) Manufacture of photosensitive coloring resin composition III-G11~III-G14, III-33 for color filters

In the examples III-11 to III-12 and III-33, the color material dispersion liquid III-G2 was used instead of the color material dispersion liquid III-G1 in (2) of Example III-1, and The photoinitiator was changed to the same as the one described in Table 13 except that the photoinitiator was changed, and the photosensitive colored resin compositions for color filters III-G11 to III-G12 and III-G33 were obtained. .

Further, in Example III-13, the above color material dispersion liquid III-G2 was used instead of the color material dispersion liquid III-G1 in (2) of Example III-1, and further substituted for Example III-1. Ethyl ketone in (2), 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-ethylindenyl) 0.02 Parts by mass, changed to 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (photoinitiator: trade name: IRGACURE 907, manufactured by BASF Co., Ltd.) 0.10 parts by mass and 2-benzyl-2-dimethylamino-1-(4- Photosensitive property of color filter was obtained in the same manner as (2) of Example III-1 except that the morphyl phenyl)-butanone-1 (photoinitiator: trade name: IRGACURE 369, manufactured by BASF) was 0.05 parts by mass. Colored resin composition III-G13.

Further, in Example III-14, the above-described color material dispersion liquid III-G2 was used instead of the color material dispersion liquid III-G1 of (2) of Example 1, and the alkali-soluble resin A solution as an alkali-soluble resin was further substituted. It is changed to an alkali-soluble resin B solution (epoxy (meth) acrylate resin having a carboxyl group in a hydrazine structure, model INR-16M, manufactured by Nagase ChemteX Co., Ltd.), and is made into the same mass by solid content. The photosensitive colored resin composition III-G14 for color filters was obtained in the same manner as (2) of Example III-1 except that the amount of use was adjusted.

(3) Formation of colored layer

In the third embodiment of the present invention, except for the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G11 to III-G14 and III-G33 are used, respectively. (3) of Example III-1 was carried out in the same manner to obtain colored layers III-G11 to III-G14 and III-G33.

Here, the abbreviations in the table are as follows.

G36: C.I. Pigment Green 36 (trade name: FASTOGEN GREEN 2YK-50, manufactured by DIC Corporation)

Y138: C.I. Pigment Yellow 138 (trade name: CHROMOFINE YELLOW 6206EC, manufactured by Dairi Seiki Co., Ltd.)

Further, G58, G7, byk-2000, N21116, byk-161, PB822, NCI-831, TR-PBG-304, OXE03, and NCI-930 are the same as those of the embodiment II series.

(Examples III-15 to III-20, Comparative Examples III-C6 to III-C8) (1) Manufacture of color material dispersions III-G15~III-G20, III-CG6~III-CG8

In (1) of Example III-1, the type and amount of the color material were changed as shown in Table 14, and the type and amount of the dispersing agent were changed so that the solid content became the same mass portion, and the total amount became The color material dispersions III-G15 to III-G20 and III-CG6 to III-CG8 were obtained in the same manner as in (1) of Example III-1 except that the amount of PGMEA was adjusted in a manner of 100 parts by mass.

(2) Manufacture of photosensitive colored resin compositions III-G15~III-G20 and III-CG6~III-CG8 for color filters

In addition to replacing the color material dispersion III-G1 in (2) of Example III-1, the above-described color material dispersions III-G15 to III-G20 and III-CG6 to III-CG8 were respectively used, and in order to increase the film thickness The amount of the alkali-soluble resin was changed to 2.80 μm, and the P/V ratio was changed to the value shown in Table 14 except that the amount of the P/V ratio was changed to the value shown in Table 14 to obtain a color filter for photosensitive coloring. Resin composition III-G15~III-G20, III-CG6~III-CG8.

(3) Formation of colored layer

In the third embodiment of the present invention, except for the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G15 to III-G20 and III-CG6 to III-CG8 are used. The rest was carried out in the same manner as in (3) of Example III-1 to obtain colored layers III-G15 to III-G20 and III-CG6 to III-CG8. Further, in Comparative Example III-C8 in which PG58 was used as the color material, the chromaticity of y=0.610 and x=0.210 under the C light source could not be achieved.

Here, the abbreviations in the table are as follows.

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

Ni-azo-1: a derivative pigment of C.I. Pigment Yellow 150 prepared by the following preparation example (Ni:Zn=1:1 (mole ratio) azo pigment)

(Modulation example)

After 550 g of distilled water, 23.1 g of diazo barbituric acid and 19.2 g of barbituric acid were introduced. Subsequently, it was adjusted to become azo barbituric acid (0.3 mol) using an aqueous potassium hydroxide solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added by dropwise addition. Thereafter, 38.7 g of melamine was introduced. Next, a 0.3 mol nickel chloride solution was mixed with a 0.3 mol zinc chloride solution, and stirred at a temperature of 80 ° C for 8 hours. The pigment was separated by filtration, washed, dried at 120 ° C, and ground in a mortar to obtain a derivative pigment of C.I. Pigment Yellow 150.

(Examples III-21 to III-25, Comparative Examples III-C9) Manufacture of color material dispersions III-G21~III-G25, III-CG9

In (1) of the example III-1, the types and amounts of the color materials are changed, and the type and amount of the dispersing agent are changed so that the solid parts are equal parts by mass, as shown in Table 15, respectively. The color material dispersions III-G21 to III-G25 and III-CG9 were obtained in the same manner as in (1) of Example III-1 except that the amount of PGMEA was adjusted to 100 parts by mass.

(2) Manufacture of photosensitive colored resin compositions III-G21~III-G25 and III-CG9 for color filters

In addition to replacing the color material dispersion III-G1 in (2) of Example III-1, respectively The color material dispersions III-G21 to III-G25 and III-CG9 were used, and the amount of the alkali-soluble resin was adjusted so that the P/V ratio was the value shown in Table 15 in order to make the film thickness 2.80 μm. The photosensitive colored resin compositions III-G21 to III-G25 and III-CG9 for color filters were obtained in the same manner as in (2) of Example III-1.

(3) Formation of colored layer

In the third embodiment of the present invention, except for the photosensitive colored resin composition III-G1, the photosensitive colored resin compositions III-G21 to III-G25 and III-CG9 are used, respectively. (3) of III-1 was carried out in the same manner to obtain colored layers III-G21 to III-G25 and III-CG9. Further, in Comparative Example III-C9 in which PG58 was used as the color material, the chromaticity of y=0.626 and x=0.205 under the C light source could not be achieved.

Here, the abbreviations in the table are as follows.

Y185: C.I. Pigment Yellow 185 (trade name: Paliotol (registered trademark) Yellow D1155, manufactured by BASF Corporation)

(Examples III-26 to III-28, Comparative Examples III-C10) Manufacture of color material dispersions III-G26~III-G28, III-CG10

In (1) of the embodiment III-1, the types and amounts of the color materials are changed, and the type and amount of the dispersing agent are changed so that the solid parts become the same mass parts, in total, as shown in Table 16. The color material dispersions III-G26 to III-G28 and III-CG10 were obtained in the same manner as in (1) of Example III-1 except that the amount of PGMEA was adjusted to 100 parts by mass.

(2) Manufacture of photosensitive colored resin compositions III-G26~III-G28 and III-CG10 for color filters

The color material dispersions III-G26 to III-G28 and III-CG10 were used in place of the color material dispersion III-G1 in (2) of Example III-1, and in order to make the film thickness 3.30 μm, The amount of the alkali-soluble resin was adjusted to be the same as the value shown in Table 16 except that the P/V ratio was the same as the value shown in Table 16. The photosensitive colored resin composition for color filter III- was obtained. G26~III-G28, III-CG10.

(3) Formation of colored layer

(3) of the example III-1, except that the photosensitive colored resin composition III-G1 is used, and the photosensitive colored resin compositions III-G26 to III-G28 and III-CG10 are used, respectively. (3) of Example III-1 was carried out in the same manner to obtain colored layers III-G26 to III-G28 and III-CG10.

(Examples III-29 to III-31, Comparative Examples III-C11) Manufacture of color material dispersions III-G29~III-G31, III-CG11

In (1) of Example III-1, the types and amounts of the color materials were changed, and the type and amount of the dispersing agent were changed so that the solid parts became the same mass parts, as shown in Table 17, respectively. The color material dispersions III-G29 to III-G31 and III-CG11 were obtained in the same manner as in (1) of Example III-1 except that the amount of PGMEA was adjusted to 100 parts by mass.

(2) Photosensitive colored resin compositions for color filters III-G29~III-G31, III-CG11 Manufacturing

The color material dispersions III-G29 to III-G31 and III-CG11 were used in place of the color material dispersion III-G1 in (2) of Example III-1, and the film thickness was 3.30 μm. The amount of the alkali-soluble resin was adjusted, and the P/V ratio was changed to the value shown in Table 17, and the same procedure as in (2) of Example III-1 was carried out to obtain a photosensitive colored resin composition III for a color filter. G29~III-G31, III-CG11.

(3) Formation of colored layer

(3) of the example III-1, except that the photosensitive coloring resin composition III-G1 is used, and the photosensitive colored resin compositions III-G29 to III-G31 and III-CG11 are used, respectively. (3) of Example III-1 was carried out in the same manner to obtain colored layers III-G29 to III-G31 and III-CG11.

(Examples III-32) (1) Manufacture of color material dispersion

6.22 parts by mass of a dispersant b solution as a dispersing agent, 13 parts by mass of CI Pigment Green 59 (PG59, trade name: FASTOGEN GREEN C100 DIC), 14.59 parts by mass of an alkali-soluble resin A solution, PGMEA 66. 20 parts by mass and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle, and pulverized by a pigment shaker (made by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, followed by removal of a particle size of 2.0 mm. Zirconium beads were added to 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm, and were similarly dispersed by a pigment shaker for 4 hours to form a green color dispersion liquid g.

6.22 parts by mass of a dispersant b solution as a dispersing agent, CI Pigment Yellow 138 (PY138, trade name: CHROMOFINE YELLOW 6206EC, manufactured by Dairi Seiki Co., Ltd.) as a color material, 13 parts by mass, and an alkali-soluble resin A solution 14.59 100 parts by mass of PGMEA, 66.20 parts by mass, and 2.0 mm zirconia beads, placed in a milk bottle, shaken for 1 hour with a pigment shaker (made by Asada Iron Works Co., Ltd.), and then taken out. The zirconia beads having a particle diameter of 2.0 mm were added to 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm, and similarly dispersed by a pigment shaker for 4 hours to be officially pulverized to obtain a yellow color material dispersion y.

(2) Manufacture of photosensitive colored resin composition III-G32 for color filters

4.67 parts by mass of the green color material dispersion liquid g obtained in the above (1), 6.73 parts by mass of the yellow color material dispersion liquid y, 0.64 parts by mass of the alkali-soluble resin A solution, and a polyfunctional monomer (trade name: ARONIX M-403, East Asia) 0.60 parts by mass of 2-methyl-1-(4-methylthiophenyl)-2- Orolinylpropan-1-one (photoinitiator: trade name: IRGACURE 907, manufactured by BASF Co., Ltd.), 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (light initiator: trade name IRGACURE 369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-, 1-(o-ethylindenyl) (photoinitiator: trade name: ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (product) 0.07 parts by mass of MEGAFACE F559, manufactured by DIC Co., Ltd., and 7.14 parts by mass of PGMEA, and a photosensitive colored resin composition III-G32 for a color filter was obtained.

(3) Formation of colored layer

(3) of the example III-1, except that the photosensitive colored resin composition III-G1 is used instead of the photosensitive colored resin composition III-G32, (3) of Example III-1 was carried out in the same manner to obtain a colored layer III-G32.

The photosensitive colored resin composition III-G32 for the obtained color filter has the same composition as the photosensitive colored resin composition III-G2 for the color filter of Example III-2, and the photosensitive colored resin for the color filter. The evaluation results of the composition III-G32 and the coloring layer III-G32 were the same as those of the photosensitive colored resin composition III-G2 and the coloring layer III-G2 for a color filter.

[Evaluation method of the series III]

The optical performance evaluation, the comparative evaluation, and the display failure evaluation were performed as follows. The evaluation of the dispersibility of the color material dispersion, the evaluation of the solvent resolubility, the evaluation of the development residue, the evaluation of the development adhesion, the evaluation of the development resistance, and the evaluation of the water permeation were carried out in the same manner as in the Example II series.

<Optical performance evaluation, comparative evaluation>

The contrast and chromaticity (x, y) and luminance (Y) of the coloring layers obtained in the examples and the comparative examples were measured using a kettle 坂 electrical comparison measuring device CT-1B and an Olympus microscopic spectroscopy measuring device OSP-SP200.

Further, in Comparative Example 8 in which PG58 was used as the color material, the chromaticity of y=0.610 and x=0.210 under the C light source could not be achieved. In Comparative Example 9 in which PG58 was used as the color material, the chromaticity of y=0.626 and x=0.205 under the C light source could not be achieved.

(Comparative evaluation benchmark) ‧Set to the value of y=0.570 and x=0.260 for C light source

A: More than 12000

B: 12000~10000

C: less than 10000

<display bad evaluation>

The display failure evaluation of the coloring layer obtained in the examples and the comparative examples was carried out by using a dielectric impedance measuring system 126096W (manufactured by Toyo Technologies Co., Ltd.).

(displays bad evaluation criteria)

A: The loss factor (tan δ) at 100 Hz is less than 0.023

B: The loss factor (tan δ) at 100 Hz is 0.023 to 0.048

C: loss factor (tan δ) at 100 Hz exceeds 0.048

If the evaluation criteria are A or B, it is practical, and if the evaluation result is A, the adverse inhibition effect is high.

[Example III system integration]

From the results of Tables 13-17, it is apparent that the color material dispersion of the embodiment of the PG59 and the yellow color material which is a dispersant combination of the polymer having the structural unit represented by the general formula (I) is stable in viscosity. Good sex. On the other hand, in the color material dispersion liquid of Comparative Example III-C4 to III-C5 in which PG59 was combined with a urethane dispersant or a polyester dispersant, the viscosity stability was remarkably deteriorated. Further, in PG58 or PG7 or PG36, the color material dispersions of Comparative Examples III-C1, III-C2 and III-C3 which are a dispersant belonging to a polymer having a structural unit represented by the general formula (I), have a viscosity. The stability was significantly worse than Example III-1 in which the same dispersant was combined. Further, in the PG7 or PG36, the dispersing liquids of Comparative Examples III-C2 and III-C3 which are a dispersing agent which is a polymer having a structural unit represented by the general formula (I) are deteriorated in dispersibility.

It is obvious from Table 13 that the yellow color material is combined with PG59. The photosensitive colored resin composition for color filters of Examples III-1 to III-14 which are a dispersant combination of a polymer having a structural unit represented by the general formula (I) can be displayed when y=0.570 A region of x=0.260, and suppressing the occurrence of poor display, can form a high-luminance coloring layer. Further, it is apparent that the color filter for the color filters of the examples III-1 to III-14 in which the PG59 is combined with the yellow color material PY138 and the dispersant belonging to the polymer having the structural unit represented by the general formula (I) is used. As the coloring resin composition, it is apparent that the dispersion stability of the color material is good, the contrast is excellent, the solvent resolubility is excellent, and the occurrence of development residue is suppressed.

Wherein, as the dispersing agent, a block copolymer having an A block comprising the structural unit represented by the above general formula (I) and a B block having a solvophilic component derived from a constituent unit of the carboxyl group-containing monomer; or a salt type block copolymer in which at least a part of a nitrogen portion of the constituent unit represented by the general formula (I) forms a salt; and the acid value of the dispersant is 1 mgKOH/g or more and 18 mgKOH/g or less, and the dispersing agent In Examples III-2, III-4, III-8, III-11 to III-14, and III-33, which have a glass transition temperature of 30 ° C or more, the development residue is particularly suppressed, and the development adhesiveness is suppressed. Excellent. Further, Example III-14 using an epoxy group-containing (meth) acrylate resin having a carboxyl group as the alkali-soluble resin in the photosensitive colored resin composition was developed in the same manner as in Example III-2. It is more excellent in adhesion, development resistance, and water permeation inhibition effect.

Further, in the examples, from the comparison of Examples III-2, III-11, III-12, III-13 and III-33, it is apparent that the use of an oxime ester photoinitiator as a photoinitiator is carried out. For example, the development resistance and the effect of inhibiting water permeation become high.

Further, it is apparent from Tables 14 and 15 that when the PG59 is combined with a yellow color material and a dispersant belonging to a polymer having a structural unit represented by the general formula (I), the color reproduction region is broadened, and y=0.570~ In the case of 0.626, the color of x=0.205~0.324 can still be displayed. The degree region, and further, under the chromaticity region showing y=0.659, can significantly suppress the occurrence of display defects, and can form a high-luminance coloring layer.

Further, in Example III-27 of Table 16, if PG58 was further combined in PG59 and yellow color material, it was compared with Example III-26 in which PG59 was used as a green color material alone, or PG58 and Y138 were combined. In Comparative Example III-C10, it is apparent that the above P/V ratio is lowered and the luminance is further improved. In Example III-28, when PG59 and PG58 as green color materials and PY138 and PY150 as yellow color materials were combined, it was apparent that the above P/V ratio was further lowered.

Further, in Example III-30 of Table 17, if PG7 was further combined with PG59 and yellow color material, the above P/V ratio was remarkably reduced as compared with Comparative Example III-C11 in which PG58 and Y138 were combined. And the brightness is also improved. In Example III-31, when PG59 and PG7 as green color materials and PY138 and PY150 as yellow color materials were combined, it was apparent that the above P/V ratio was further lowered.

On the other hand, as shown in Comparative Example III-C1, when PG58 is used, when y=0.570, a region of x=0.260 can be displayed, but display failure occurs, and the luminance is inferior to that in the case of using PG59. Moreover, the development residue is also deteriorated. Further, as shown in Comparative Examples III-C2 and III-C3, when PG7 or PG36 is used, when y=0.570, the region of x=0.260 can be displayed, but the luminance is low. Further, even if a dispersant belonging to a polymer having a structural unit represented by the general formula (I) is used in combination, the dispersibility is deteriorated, so that the contrast is low, and the resolubility and the residue are also deteriorated.

On the other hand, the photosensitive colored resin composition for color filters of Comparative Example III-C4 to III-C5 in which PG59 is combined with a urethane dispersant or a polyester dispersant is dispersed. Since the properties are deteriorated, the luminance is lowered and the contrast is low as compared with the examples, and the resolubility and the residue are also deteriorated.

Embodiment IV Series: Second Embodiment of the Third Embodiment of the Invention

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

(Example IV-1) (1) Manufacture of color material dispersion IV-G1

6.22 parts by mass of a dispersant a solution as a dispersing agent, 6.42 parts by mass of CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) as a color material, and CI Pigment Blue 15:4 as a blue color material. (PB15:4, trade name: CYANINE BLUE CP-1, manufactured by Dairi Seiki Co., Ltd.) 1.39 parts by mass, CI Pigment Yellow 139 as a yellow color material (PY139, trade name IRGAPHOR YELLOW 2R-CF, manufactured by BASF) 1.40 parts by mass and CI Pigment Yellow 150 (PY150, trade name: LEVASCREEN YELLOW G04, manufactured by LAXESS Co., Ltd.) 3.80 parts by mass, alkali-soluble resin A solution 14.59 parts by mass, PGMEA 66.20 parts by mass, and 2.0 mm zirconia beads 100 parts by mass of the ball was placed in a milk bottle, shaken with a pigment shaker (made by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary crushing, and then a zirconia ball having a particle diameter of 2.0 mm was taken out, and a zirconia having a particle diameter of 0.1 mm was added. 200 parts by mass of the beads were similarly dispersed by a pigment shaker for 4 hours to form a solid dispersion, and a color material dispersion IV-G1 was obtained.

(2) Manufacture of photosensitive colored resin composition IV-G1 for color filters

11.41 parts by mass of the color material dispersion liquid IV-G1 obtained in the above (1), 2.75 parts by mass of the alkali-soluble resin A solution, and 0.60 mass of a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd.) , 2-methyl-1-(4-methylthiophenyl)-2- Orolinylpropan-1-one (photoinitiator: trade name: IRGACURE 907, manufactured by BASF Co., Ltd.), 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (light initiator: trade name IRGACURE 369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-, 1-(o-ethylindenyl) (photoinitiator: trade name: ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (product) 0.07 parts by mass of MEGAFACE F559, manufactured by DIC Co., Ltd., and 9.72 parts by mass of PGMEA, and a photosensitive colored resin composition IV-G1 for a color filter was obtained.

(3) Formation of colored layer

The photosensitive colored resin composition IV-G1 obtained in the above (2) was applied to a glass substrate ("NA35", manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and 100 mm × 100 mm, respectively, using a spin coater. After coating, it was dried at 80 ° C for 3 minutes using a hot plate, irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp, and post-baked for 30 minutes in a dust-free oven at 230 ° C, and the film thickness after hardening became 2.80 μm. The film thickness is adjusted to form the color layer IV-G1.

(Examples IV-2 to IV-10, IV-15 to IV-17, Comparative Examples IV-C1 to IV-C4) (1) Manufacture of color material dispersions IV-G2~IV-G10, IV-G15~IV-G17, IV-CG1~IV-CG4

In Examples IV-2 to IV-10 and Comparative Examples IV-C3 to IV-C4, in (1) of Example IV-1, except that the dispersant a solution was replaced as shown in Table 18, The type and amount of the dispersing agent are changed so that the solid content becomes the same mass portion, and the total amount becomes The color material dispersions IV-G2 to IV-G10 and IV-CG3 to IV-CG4 were obtained in the same manner as in (1) of Example IV-1 except that the amount of PGMEA was adjusted in a manner of 100 parts by mass. In the examples IV-15 to IV-17, in the example (1) of the example IV-1, the dispersant b solution was used instead of the dispersant a solution, and the color material was further changed to obtain 100 parts by mass in total. The color material dispersions IV-G15 to IV-G17 were obtained in the same manner as in (1) of Example IV-1 except that the amount of PGMEA was adjusted. In Comparative Example IV-C1 to IV-C2, in (1) of Example IV-1, except that the color material was changed, the same procedure as in (1) of Example IV-1 was carried out to obtain IV-CG1 to IV. -CG2.

(2) Manufacture of photosensitive colored resin compositions IV-G2~IV-G10, IV-G15~IV-G17, IV-CG1~IV-CG4 for color filters

The color material dispersions IV-G2 to IV-G10, IV-G15 to IV-G17, and IV-CG1 to IV were respectively used in place of the color material dispersion IV-G1 in (2) of Example IV-1. - CG4, and in order to adjust the thickness of the alkali-soluble resin to 2.8 μm, the P/V ratio was changed to the value shown in Table 18, and the same procedure as in (2) of Example IV-1 was carried out. The photosensitive coloring resin compositions for color filters are IV-G2 to IV-G10, IV-G15 to IV-G17, and IV-CG1 to IV-CG4.

(3) Formation of colored layer

In the (3) of the embodiment IV-1, the photosensitive colored resin compositions IV-G2 to IV-G10 and IV-G15 to IV-G17 are used in addition to the photosensitive coloring resin composition IV-G1. Other than IV-CG1 to IV-CG4, the same procedure as in (3) of Example IV-1 was carried out to obtain colored layers IV-G2 to IV-G10, IV-G15 to IV-G17, and IV-CG1 to IV-CG4.

(Examples IV-11~IV-14, IV-36) (1) Manufacture of photosensitive colored resin compositions IV-G11~IV-G14 and IV-G36 for color filters

In the examples IV-11 to IV-12 and IV-36, in addition to the color material dispersion IV-G1 in the substitution of the embodiment (II), the color material dispersion IV-G2 was used, and The photoinitiator was changed to the same as the one described in Table 18, and the photosensitive colored resin compositions for color filters IV-G11 to IV-G12 and IV-G36 were obtained in the same manner as in the example (II) of Example IV-1. .

Further, in Example IV-13, the above-described color material dispersion liquid IV-G2 was used instead of the color material dispersion liquid IV-G1 in (2) of Example IV-1, and further substituted for Example IV-1 ( 2) Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-ethylindenyl) 0.02 mass Change to 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (photoinitiator: trade name: IRGACURE 907, manufactured by BASF Co., Ltd.) 0.10 parts by mass and 2-benzyl-2-dimethylamino-1-(4- Photosensitive property of color filter was obtained in the same manner as (2) of Example IV-1 except that the morphyl phenyl)-butanone-1 (light-based initiator: trade name: IRGACURE 369, manufactured by BASF) was 0.05 parts by mass. Colored resin composition IV-G13.

Further, in Example IV-14, the color material dispersion liquid IV-G2 was used instead of the color material dispersion liquid IV-G1 of (II) of Example IV-1, and the alkali-soluble resin A as an alkali-soluble resin was further substituted. The solution was changed to an alkali-soluble resin B solution (an epoxy group (meth) acrylate resin having a carboxyl group in a hydrazine structure, model number INR-16M, manufactured by Nagase ChemteX Co., Ltd.), and the same mass parts were obtained according to the solid content. The photosensitive colored resin composition IV-G14 for color filters was obtained in the same manner as (2) of Example IV-1 except that the amount of use was adjusted.

(3) Formation of colored layer

In the example (3) of the example IV-1, the photosensitive coloring resin composition IV-G1 was used instead of the photosensitive colored resin compositions IV-G11 to IV-G14 and IV-G36, respectively. (3) of IV-1 was carried out in the same manner to obtain colored layers IV-G11 to IV-G14 and IV-G36.

Here, the abbreviations in the table are as follows.

PB15:4:C.I. Pigment Blue 15:4 (trade name: CYANINE BLUE CP-1, manufactured by Dairi Seiki Co., Ltd.)

PB15:3:C.I. Pigment Blue 15:3 (trade name: CHROMOFINE BLUE A-220JC, manufactured by Dairi Seiki Co., Ltd.)

Further, G36, G58, Ni-azo-1, Y138, byk-2000, N21116, byk-161, PB822, NCI-831, TR-PBG-304, OXE03, NCI-930 are the same as the embodiment II or III series. .

(Examples IV-18 to IV-19, Comparative Examples IV-C5 to IV-C13) (1) Manufacture of color material dispersions IV-G18~IV-G19, IV-CG5~IV-CG13

In the case of (1) of the example IV-1, the type and amount of the color material were changed as shown in Table 19, and the type and amount of the dispersing agent were changed to the same mass parts as the solid content, and the total amount was 100. The color material dispersions IV-G18 to IV-G19 and IV-CG5 to IV-CG13 were obtained in the same manner as in (1) of Example IV-1 except that the amount of the PGMEA was adjusted in a mass ratio.

(2) Manufacture of photosensitive colored resin compositions IV-G18~IV-G19, IV-CG5~IV-CG13 for color filters

The color material dispersions IV-G18 to IV-G19, IV-CG6, IV-CG7, and IV-CG12 to IV were respectively used in place of the color material dispersion liquid IV-G1 in (2) of Example IV-1. - CG13, and in order to adjust the thickness of the alkali-soluble resin to 2.8 μm, the P/V ratio was changed to the value shown in Table 19, and the color was obtained in the same manner as in (2) of Example IV-1. The photosensitive coloring resin compositions for the filters were IV-G18 to IV-G19, IV-CG6, IV-CG7, and IV-CG12 to IV-CG13.

In the color material combination of Comparative Example IV-C5 and Comparative Examples IV-C8 to IV-C11, a photosensitive colored resin composition having a film thickness of 2.8 μm and having a chromaticity of x=0.200 and y=0.710 could not be prepared.

(3) Formation of colored layer

In (3) of the embodiment IV-1, the photosensitive colored resin compositions IV-G18 to IV-G19, IV-CG6, IV-CG7 and the photosensitive photosensitive resin composition IV-G1 are used, respectively. Other than IV-CG12 to IV-CG13, the same procedure as in (3) of Example IV-1 was carried out to obtain colored layers IV-G18 to IV-G19, IV-CG6, IV-CG7 and IV-CG12 to IV-CG13.

PB15:6:C.I. Pigment Blue 15:6 (trade name FASTOGEN BLUE A510, DIC (share) system)

(Examples IV-20 to IV-34, Comparative Examples IV-C14 to IV-C16) Manufacture of color material dispersions IV-G20~IV-G34, IV-CG14~IV-CG16

In (1) of the example IV-1, the color material type and the amount of use are changed, and the type and amount of the dispersing agent are changed so that the solid content becomes the same mass part, in total, as shown in Table 20, respectively. The color material dispersions IV-G20 to IV-G34 and IV-CG14 to IV-CG16 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.

(2) Manufacture of photosensitive colored resin compositions IV-G20~IV-G34 and IV-CG14~IV-CG16 for color filters

In order to replace the color material dispersion liquid IV-G1 in (2) of Example IV-1, the above-described color material dispersions IV-G20 to IV-G34, IV-CG14 to IV-CG16 were respectively used, and in order to increase the film thickness The amount of the alkali-soluble resin was adjusted to 2.8 μm, and the P/V ratio was changed to the value shown in Table 20, and the same procedure as in (2) of Example IV-1 was carried out to obtain a photosensitive colored resin for a color filter. Compositions IV-G20~IV-G34, IV-CG14~IV-CG16.

(3) Formation of colored layer

In the third embodiment of the present invention, except for the photosensitive colored resin composition IV-G1, the photosensitive colored resin compositions IV-G20 to IV-G34 and IV-CG14 to IV-CG16 are used. The rest was carried out in the same manner as in (3) of Example IV-1 to obtain colored layers IV-G20 to IV-G34 and IV-CG14 to IV-CG16.

Further, G7 and Y185 are the same as in the embodiment III series.

(Examples IV-35) (1) Manufacture of color material dispersion

6.22 parts by mass of a dispersant b solution as a dispersing agent, 13 parts by mass of CI Pigment Green 59 (PG59, trade name: FASTOGEN GREEN C100 DIC), 14.59 parts by mass of an alkali-soluble resin A solution, PGMEA 66. 20 parts by mass and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were placed in a milk bottle, and pulverized by a pigment shaker (made by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, followed by removal of a particle size of 2.0 mm. Zirconium beads were added to 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm, and were similarly dispersed by a pigment shaker for 4 hours to form a green color dispersion liquid g.

In the above-mentioned green color material dispersion liquid g, except for replacing 13 parts by mass of CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) as a color material, CI Pigment Blue 15:4 (PB15:4) was used. Product name: CYANINE BLUE CP-1, manufactured by Dairi Seiki Co., Ltd.) 13 parts by mass is used as the color material, and the blue color material dispersion liquid b is obtained in the same manner as the above-described green color material dispersion liquid g.

In the above-mentioned green color material dispersion liquid g, except for replacing 13 parts by mass of CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC), which is a color material, CI Pigment Yellow 139 (PY139, trade name: 13 parts by mass of IRGAPHOR YELLOW 2R-CF, manufactured by BASF, was carried out in the same manner as the green color material dispersion liquid g except for the color material, to obtain a yellow color material dispersion liquid y1.

In the above-mentioned green color material dispersion liquid g, except for replacing 13 parts by mass of CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC), which is a color material, CI Pigment Yellow 150 (PY150, trade name: LEVASCREEN YELLOW 13 parts by mass of G04, manufactured by LAXESS Co., Ltd., as a color material, was carried out in the same manner as the above-described green color material dispersion liquid g to obtain a yellow color material dispersion liquid y2.

(2) Manufacture of photosensitive colored resin composition IV-G35 for color filters

5.63 parts by mass of the green material dispersion liquid g obtained in the above (1), 1.22 parts by mass of the blue color material dispersion liquid b, 1.23 parts by mass of the yellow color material dispersion liquid y1, 3.33 parts by mass of the yellow color material dispersion liquid y2, and Synthesis Example 9. 2.75 parts by mass of a base-soluble resin A solution, a polyfunctional monomer (trade name: ARONIX M-403, manufactured by Toagosei Co., Ltd.) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl) )-2- Orolinylpropan-1-one (photoinitiator: trade name: IRGACURE 907, manufactured by BASF Co., Ltd.), 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (light initiator: trade name IRGACURE 369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-, 1-(o-ethylindenyl) (photoinitiator: trade name: ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (product) 0.07 parts by mass of MEGAFACE F559, manufactured by DIC Co., Ltd., and 9.72 parts by mass of PGMEA, and a photosensitive colored resin composition IV-G35 for a color filter was obtained.

(3) Formation of colored layer

(3) of the example IV-1, except that the photosensitive colored resin composition IV-G1 was used instead of the photosensitive colored resin composition IV-G35, the same as the above (3) of the example IV-1. This was carried out to obtain a colored layer IV-G35.

The photosensitive colored resin composition IV-G35 for the obtained color filter has the same composition as the photosensitive colored resin composition IV-G2 for the color filter of Example IV-2, and the photosensitive colored resin for the color filter. The evaluation results of the composition IV-G35 and the coloring layer IV-G35 are the photosensitive coloring resin composition IV-G2 and the coloring layer for the color filter. The evaluation results of IV-G2 are the same.

[Evaluation Method of Example IV Series]

The optical performance evaluation and the comparative evaluation were carried out as follows. The dispersibility evaluation, the display failure evaluation, the solvent resolubility evaluation, the development residue evaluation, the development adhesion evaluation, the development resistance evaluation, and the water permeation evaluation of the color material dispersion were evaluated in the same manner as in the Example II series.

<Optical performance evaluation, comparative evaluation>

The contrast and chromaticity (x, y) and luminance (Y) of the coloring layers obtained in the examples and the comparative examples were measured using a kettle 坂 electrical comparison measuring device CT-1B and an Olympus microscopic spectroscopy measuring device OSP-SP200.

(Comparative evaluation benchmark) ‧Set to the value of y=0.670 and x=0.210 under C light source

A: More than 8000

B: 6000~8000

C: less than 6000

[Example III system integration]

From the results of Tables 18 to 20, it is apparent that the color material of the embodiment in which PG59 and the blue color material and the above-mentioned specific yellow color material are combined with a dispersant which is a polymer having a structural unit represented by the general formula (I) The dispersion has a markedly good viscosity stability. On the other hand, in the color material dispersion liquid of Comparative Examples IV-C3 to IV-C4 in which the urethane-based dispersing agent or the polyester-based dispersing agent was combined with PG59, the viscosity stability was remarkably deteriorated. Also, on PG58 Or the color material dispersion liquid of Comparative Examples IV-C1 and IV-C2 which are a dispersant combination of a polymer having a structural unit represented by the general formula (I) in PG36, and the viscosity stability thereof is remarkably higher than that of the same dispersing agent. Example IV-1 was poor. Further, in PG36, the color material dispersion liquid of Comparative Example IV-C2 in which the dispersant belonging to the polymer having the structural unit represented by the general formula (I) was combined was deteriorated in dispersibility.

As is apparent from Table 18, Examples IV-1 to IV-17 and IV in which PG59 combines a blue color material with the above specific yellow color material and a dispersant which is a combination of a polymer having a structural unit represented by the general formula (I). The photosensitive coloring resin composition for a color filter of -36 is a region of x=0.210 when y=0.670, and suppresses the occurrence of display defects, thereby forming a high-luminance coloring layer. Further, it is apparent that the photosensitive coloring resin composition for color filters of the examples IV-1 to IV-17 and IV-36 is excellent in dispersion stability of the color material, excellent in contrast, and excellent in solvent resolubility, and further The occurrence of development residue is suppressed.

Wherein, as the dispersing agent, a block copolymer having an A block comprising the structural unit represented by the above general formula (I) and a B block having a solvophilic component derived from a constituent unit of the carboxyl group-containing monomer; or a salt type block copolymer in which at least a part of a nitrogen portion of the constituent unit represented by the general formula (I) forms a salt; and the acid value of the dispersant is 1 mgKOH/g or more and 18 mgKOH/g or less, and the dispersing agent A dispersing agent having a glass transition temperature of 30 ° C or higher, particularly suppressing the occurrence of development residue, and excellent development adhesiveness (Example IV in Examples IV-1 to IV-17 and IV-36 having the same P/V ratio) 2. IV-4, IV-8, IV-11~IV-1 and IV-36). Further, Example IV-14 using an epoxy group-containing (meth) acrylate resin having a carboxyl group as the alkali-soluble resin in the photosensitive colored resin composition was developed in Comparative Example IV-2. It is superior in adhesion, development resistance and water bleeding inhibition.

Further, in the examples, Examples IV-2, IV-11, IV-12, IV-13 and IV-36 In comparison, it is apparent that the use of the oxime ester photoinitiator as a photoinitiator has a markedly higher development resistance and water permeation inhibition effect.

Further, as apparent from Tables 19 and 20, when the PG59 is combined with the blue color material and the specific yellow color material and the dispersant belonging to the polymer having the structural unit represented by the general formula (I), the color reproduction domain is broadened. In the case of y=0.570~0.720, the chromaticity region of x=0.140~0.265 can still be displayed, and the occurrence of display failure can be obviously suppressed under the chromaticity region showing y=0.750, which can be formed. The color layer of higher brightness.

Further, in the embodiment IV-33 of Table 20, if the blue color material and the specific yellow color material are combined in PG59 and PG7 is further combined, the above-mentioned Example IV-32 can be achieved as compared with Example IV-32 which achieves the same color tone. The P/V ratio is reduced and the luminance is also significantly improved.

On the other hand, as shown in Comparative Example IV-C1, even if the blue color material and the specific yellow color material are combined in the same manner as the embodiment, if PG58 is used, the area of x=0.210 can be displayed at y=0.670. However, the display is poor, and its luminance is inferior to that of the PG59. Further, the development residue or the development adhesiveness is also deteriorated. Further, as shown in Comparative Example IV-C2, even if the blue color material and the specific yellow color material were combined in the same manner as in the example, when PG36 was used, the area of x=0.210 could be displayed when y=0.670. Poor display, low brightness. Further, even if a dispersant belonging to a polymer having a structural unit represented by the general formula (I) is combined, the dispersibility is not good, so that the contrast is low, and the resolubility, development residue, and development adhesiveness are also deteriorated.

On the other hand, in Comparative Example IV-C3 to IV-C4 in which PG59 was combined with a blue color material and a specific yellow color material, and further a urethane dispersant or a polyester dispersant was combined. The photosensitive colored resin composition for a color filter is degraded in dispersibility, so that the luminance is lowered compared with the embodiment, and the contrast is low, and the resolubility and the development residue are low. The slag is also degraded.

As shown in Comparative Examples IV-C5, IV-C8, and IV-C11 of Table 19, in the composition using G58, the blue color material was not combined, and the yellow color material was combined, the film thickness 2.8 μm could not be modulated, and x= could be realized. A photosensitive colored resin composition having a chromaticity of 0.200 and y = 0.710. Further, in the combination of the color materials of Comparative Examples IV-C9 and IV-C10, it was not possible to prepare a photosensitive colored resin composition having a film thickness of 2.8 μm and a chromaticity of x=0.200 and y=0.710.

As shown in Comparative Examples IV-C6 and IV-C13, if the blue color material and the yellow color material containing PY139 are combined in G58, the chromaticity of the film thickness of 2.8 μm, x=0.200, and y=0.710 can be achieved, but occurs. The display is poor, the luminance is deteriorated, and the development residue or the development adhesiveness is also deteriorated.

As shown in Comparative Examples IV-C7 and IV-C12, if the green color material, the blue color material, and the yellow color material are not used, the chromaticity of the film thickness of 2.8 μm, x=0.200, and y=0.710 can be achieved, and In Comparative Example IV-C7, which has a poor display, but the blue color material is significantly deteriorated to such an extent that it cannot reach the practical level, and the yellow color material is more and the luminance is higher. Comparative Example IV-C12 is a development residue or development adhesive. Sexual deterioration.

In Comparative Example IV-C14 of Table 20, an example corresponding to the color tone of Example IV-24 was realized by using G36, but display failure and luminance deterioration occurred, and re-solubility, development residue, and development adhesiveness were also deteriorated.

In Comparative Example IV-C15, an example corresponding to the color tone of Example IV-34 was obtained using G36, but the luminance was deteriorated, and the resolubility, development residue, and development adhesiveness were also deteriorated.

Comparative Examples IV-C16 used G58 to achieve an example of the color tone corresponding to Examples IV-32 and IV-33, but the luminance was deteriorated, and the resolubility, development residue, and development adhesion were also deteriorated.

Claims (10)

A color material dispersion liquid for a color filter, comprising a color material, a dispersant, and a solvent; wherein the dispersant is a block copolymer (P1) and a salt block copolymer (P2) At least one of; P1: a block copolymer having an A block comprising a structural unit represented by the following general formula (I) and a B block comprising a constituent unit derived from a carboxyl group-containing monomer; P2: the above block At least a part of the nitrogen moiety at the terminal of the structural unit represented by the above general formula (I) in the copolymer, and one or more compounds selected from the group consisting of the compounds represented by the following general formulas (1) to (3) a salt-type block copolymer of the salt; the acid value of the dispersant is 1 to 18 mg KOH / g, and the glass transition temperature of the dispersant is 30 ° C or more; (In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bond group, and R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group which may also contain a hetero atom, and R ² and R ^{3 are} also They may be bonded to each other to form a ring structure; in the general formula (1), R ^a represents ^a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent. a group, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or a carbon number of 1~ (alkyl)-linked (meth) acrylonitrile group; in general formula (2), R ^b , R ^{b '} and R ^b" each independently represent a hydrogen atom, an acidic group or an ester group thereof, and may have a substituent. a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or a benzyl group which may have a substituent, or -OR ^f , and R ^f 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 carbon number of 1 ~4 alkyl-linked (meth) acryloyl group, X represents Atom, a bromine atom or an iodine atom; general formula (3), R ^c and R ^d each independently represent a hydrogen atom, a hydroxyl group, a straight-chain carbon number of 1 to 20, the branched-chain or cyclic alkyl group, vinyl group, Further, a phenyl group or a benzyl group having a substituent, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, and a phenyl group which may have a substituent. Or a benzyl group or a (meth) acryl fluorenyl group bonded via an alkylene group having 1 to 4 carbon atoms; wherein at least one of R ^c and R ^d contains a carbon atom). The color material dispersion liquid for a color filter according to claim 1, wherein the block copolymer (P1) in the dispersant contains a constituent unit derived from a hydroxyl group-containing monomer. The color material dispersion liquid for a color filter according to claim 1, wherein the block copolymer (P1) in the dispersant contains at least one of the following: (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 hydroxyl group-containing and aromatic group-containing monomer. The color material dispersion liquid for a color filter according to claim 1, wherein the above salt type block In the copolymer, one mole of the nitrogen moiety at the terminal of the structural unit represented by the above general formula (I) is contained, and one or more selected from the group consisting of the compounds represented by the above general formulas (1) to (3) are contained. The compound is 0.1 to 0.7 mol. The color material dispersion liquid for a color filter according to claim 1, wherein the color material contains C.I. Pigment Green 59. A photosensitive colored resin composition for a color filter comprising the color material dispersion liquid of claim 1, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. The photosensitive coloring resin composition for a color filter according to claim 6, wherein the photoinitiator comprises an oxime ester photoinitiator. A color filter comprising at least one of a transparent substrate and a coloring layer provided on the transparent substrate, wherein at least one of the colored layers has a photosensitive colored resin for color filter of claim 6 A colored layer formed by hardening the composition. A liquid crystal display device comprising the color filter of claim 8, the counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. An organic light-emitting display device comprising the color filter of claim 8 and an organic light-emitting body.