TWI743635B - 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℃ or more:

General Formula (I)

(symbols in the formulae are as described in the Description.)

Description

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

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, organic light-emitting display devices such as organic EL displays with high visibility through self-luminescence are also attracting attention as the next-generation image display devices. Regarding the performance of these image display devices, there is a strong desire for further enhancement of image quality or reduction of power consumption, such as improvement of contrast and color reproducibility.

Most of the conventional display devices are based on sRGB (IEC61966-2-1) which is an international standard for color space. However, in order to be closer to the actual performance and to improve the color reproducibility, the display device corresponding to AdobeRGB, which has a wider color reproduction gamut than sRGB, has increased. The AdobeRGB specification is defined by the color space advocated by Adobe Systems. In AdobeRGB, the three primary color systems are as follows Determined by the chromaticity coordinates x and y in the XYZ color system. The AdobeRGB standard is characterized by a wider color reproduction gamut in the green direction than the sRGB standard.

Red: x=0.64; y=0.34

Green: x=0.21; y=0.71

Blue: x=0.15; y=0.06

In addition, there are also requirements for those complying with the DCI (Digital Cinema Initiatives) specification, which has a wider color reproduction gamut in the red and green directions than sRGB.

In these liquid crystal display devices or organic light emitting display devices, color filters are used. For example, the formation of a color image in a liquid crystal display device is by directly coloring light passing through a color filter into the color of each pixel constituting the color filter, and synthesizing these colored lights to form a color image. As the light source at this time, in addition to the conventional cold cathode ray tube, there is a case of using white light-emitting organic light-emitting elements or white light-emitting inorganic light-emitting elements. In addition, in organic light emitting display devices, color filters are used for color adjustment and the like.

Under this circumstance, expectations for high brightness or high contrast in the color filter and improvement of color reproducibility are also increasing.

Here, the color filter generally has a transparent substrate, a coloring layer formed on the transparent substrate and including coloring patterns of the three primary colors of red, green, and blue, and a light-shielding portion formed on the transparent substrate for dividing each coloring pattern.

As a method of forming pixels in a color filter, among them, from the viewpoints of spectral characteristics, durability, pattern shape, and accuracy, the most widely used method is the pigment dispersion method with uniformly superior characteristics.

In a color filter with pixels formed by the pigment dispersion method, in order to achieve high brightness or high contrast, the miniaturization of pigments is reviewed. By making the pigment fine It is believed that it can reduce the scattering of light penetrating the color filter caused by the pigment particles, and achieve high brightness or high contrast.

However, the refined pigment particles tend to agglomerate, so there is a problem of reduced dispersibility or dispersion stability.

As a method of improving the dispersion method of the finely divided pigment, it is known to be effective to use a dispersant. For example, Patent Document 1 aims to provide a coloring composition for color filters with excellent chromaticity characteristics, good developability and storage stability, which discloses coloring for color filters using a block copolymer as a pigment dispersant The composition, the block copolymerization system has: A block containing specific repeating units with amine groups or ammonium salt groups; and specific repeating units with alkylene oxide chains containing alcohols derived from carboxylic acid esters, and The B block of the repeating unit of the acidic group.

In addition, the purpose of Patent Document 2 is to provide a coloring composition for color filters that has excellent chromaticity characteristics, good developability and storage stability, and discloses a coloring composition for color filters that uses a copolymer as a pigment dispersant The copolymerization system contains: a specific repeating unit with an amine group or an ammonium salt group, a repeating unit with a carboxylic acid ester, and a repeating unit with an acidic group, the repeating unit containing the carboxylate is set to a specific ratio, and Let the ratio of weight average molecular weight and number average molecular weight be a specific ratio.

On the other hand, in the color filter, the area connecting the three points of red, green, and blue pixels becomes the limit of reproducible colors. In other words, the larger the triangle of the three pixels of red, green, and blue, the larger the color filter, the wider the range of colors that can be reproduced on the screen of the display device.

In order to achieve the above-mentioned AdobeRGB or DCI color space with a wide color reproduction gamut, it is especially required to use the green pixels of the color filter as the green degree of high color density {(x=0.14~0.30, y=0.55~0.75) , Better (x=0.14~0.30, y=0.57~0.75), Even better (x=0.14~0.30, y=0.61~0.75)} area.

Conventionally, green pigments widely used as green pixels include CI Pigment Green 7 (hereinafter sometimes referred to as PG7), CI Pigment Green 36 (hereinafter sometimes referred to as PG36), CI pigment Green 58 (hereinafter sometimes referred to as PG58).

However, when using PG7 to produce green pixels in a way that achieves the above-mentioned high color density green area, there is a problem that the brightness of the green pixels decreases. When PG7 is used as the main green color material to form green pixels, it becomes a darker color filter.

In addition, when using PG36 to produce green pixels to achieve the above-mentioned high color density green area, although it is not as serious as PG7, there is a problem that the brightness of the green pixels decreases.

In addition, if PG58 is used, the brightness will increase, but when producing green pixels including the above-mentioned high-density green areas, the green pixels must be made very thick. This is not only a problem in mass production, but because only green pixels are produced. Since the film is thickened, it is difficult to maintain the performance of the color filter. Furthermore, even if only PG58 is used, there are still areas that cannot be achieved in the high-density green area, and there is a limit in producing green pixels in a way that becomes a larger triangle.

Patent Document 3 describes the use of a colored resin composition for color filters that can achieve the target chromaticity of green with high color density without thickening the film, and can form high-brightness green pixels. The pigment of cyanine. However, higher brightness is still required.

On the other hand, Patent Document 4 aims to provide a colored curable resin composition for color filters that can suppress the occurrence of foreign matter failures caused by zinc bromide phthalocyanine pigments that have attracted attention for the formation of green pixels in recent years , Which reveals a color filter Light sheet coloring composition, which is used together as a pigment dispersant containing a specific structural unit of the amine polymer pigment dispersant, and as an agglutination inhibitor containing a structural unit with a quaternary ammonium salt group in the side chain, and without quaternary ammonium Agglomeration inhibitor for block copolymers of base structural units. However, the zinc bromide phthalocyanine pigment system described in Patent Document 4 is substantially only C.I. Pigment Green 58 (PG58), and a green pigment dispersion liquid exhibiting bluish green and high brightness cannot be obtained.

In addition, green pixels have a problem that display defects are likely to occur. More specifically, the liquid crystal display device of the horizontal electric field mode has the coloring layer of the color filter in the liquid crystal driving electric field, so it is greatly affected by the electrical characteristics of the coloring layer. In the case of using PG36 for green pixels, in the liquid crystal display device of the horizontal electric field mode, various display failures such as liquid crystal alignment disorder caused by the electrical characteristics of the green pixels, burn-in phenomenon caused by switching threshold deviation, etc. will occur. . This kind of display defect is caused by the fact that when PG58 is used for the green pixels, it occurs more remarkably and causes problems.

In Patent Document 5, in the liquid crystal display device of the horizontal electric field method, the electrical properties of the coloring layer as a color filter will not adversely affect the switching performance of the liquid crystal, and sufficient performance can be ensured even if a protective layer of transparent resin is not provided. And as a color filter that can correspond to high color reproducibility, it is revealed that the coloring layer forming the green pixel contains a specific amount of PG36 below a specific amount, and has a specific dielectric positive (tanδ) value.

However, in the technique disclosed in Patent Document 5, even if the display failure is reduced, the brightness is still insufficient, and it is also insufficient from the viewpoint of wider color reproducibility.

On the other hand, in Patent Document 6, as a green composition for color filters that can adjust brightness without reducing high contrast, it is disclosed that it contains PG58, and yellow organic pigments, and contains selected from blue pigments, red pigments, and purple. A green composition of either pigment or orange pigment.

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

[Prior Technical Literature]

[Patent Literature]

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

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

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

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

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

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

In color filters in recent years, along with the technology to improve the dispersion of color materials to achieve the requirements of high brightness or high contrast, it is necessary to solve various problems in the mass production of color filters. That is, in order to increase the color material concentration in the resin composition, it is necessary to increase the dispersant, which causes problems such as the occurrence of development residue or the delay of the development time. In addition, if the color material concentration is increased and the dispersant content is increased, the amount of the binder is relatively reduced, so that the colored resin layer is easily peeled from the base substrate during development. Therefore, although high developing adhesion is required as a colored resin composition, there is a problem that it does not reach a practical level. Furthermore, in the manufacturing steps of the color filter, it is required that the solid content of the once-dried coloring resin composition is re-dissolved in the solvent, and the re-solubility to the solvent is superior. For example, if a photosensitive colored resin composition is attached to the tip of the die lip during coating with a die coater, a cured product will be generated due to drying, and the coating will be reopened. If the cured product is not easy to dissolve in the photosensitive colored resin composition at the beginning, a part of the cured product on the die lip will peel off and will easily adhere to the colored layer of the color filter, which may cause foreign matter defects. Especially when the color material concentration of the colored resin composition is increased, the solvent resolubility is likely to be insufficient, and the production rate of the color filter is reduced due to the occurrence of the above-mentioned foreign matter in the manufacturing process of the color filter.

However, according to the methods described in Patent Documents 1 and 2, in addition to the dispersibility of color materials, all the problems in mass production of color filters, the occurrence of developing residues, developing adhesion, and solvent resolubility are as follows: It is difficult to solve them all together as shown in the comparative examples described later.

In view of the foregoing facts, the first object of the present invention is to provide a color material dispersion that has excellent color material dispersion stability, suppresses the occurrence of development residues, and can produce a photosensitive colored resin composition with excellent development adhesion and solvent resolubility. A photosensitive coloring resin composition for color filters with superior color material dispersion stability, inhibiting the occurrence of developing residues, excellent developing adhesion and solvent resolubility, and forming a color layer with superior contrast; using this color filter A color filter formed from a photosensitive colored resin composition for an optical sheet; and a liquid crystal display device and an organic light emitting display device with excellent display characteristics by using the color filter.

In addition, it is not necessary to thicken the green pixels of the color filter and create the above-mentioned high-density green chromaticity area while achieving high brightness or high contrast. Although it is desirable to have a bluish green And the green pigment dispersion liquid with high brightness, but there is no conventional knowledge.

In view of the above-mentioned facts, the second object of the present invention is to provide a green color material dispersion liquid that exhibits bluish green color, excellent color material dispersion stability, and high brightness; using the color material dispersion liquid, the solvent has excellent resolubility and high Brightness and high contrast form a photosensitive colored resin composition for color filters with excellent color reproducibility; use this A color filter with high brightness, high contrast and excellent color reproducibility of a photosensitive colored resin composition for color filters; and a liquid crystal display device with high brightness and excellent color reproducibility by using the color filter, and Organic light emitting display device.

The first color material dispersion liquid for color filters of the present invention, which is used to solve the above-mentioned first object, is a color material dispersion liquid containing a color material, a dispersant, and a solvent; it is characterized by:

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

P1: A block copolymer having an A block containing a structural unit represented by the following general formula (I) and a B block containing a structural unit derived from a carboxyl group-containing monomer;

P2: At least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) of the block copolymer is selected from the group consisting of compounds represented by the following general formulas (1) to (3) A salt-type block copolymer formed by forming a salt of more than one compound;

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

[化1]

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bonding group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, R ² and R ³ It can also be bonded to each other to form a ring structure;

In general formula (1), R ^a represents a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a phenyl group or a benzyl group which may also have a substituent, or an alkylene group with a carbon number of 1 to 4 (formaldehyde yl) Bingxi Xi group; general formula 2) (, R ^b, R ^{b 'and} R ^{b "each} independently represent a hydrogen atom, an ester group or an acidic group, may also have substituent group of carbon number 1 to 20 of a linear , Branched chain or cyclic alkyl group, vinyl group which may have substituents, phenyl group or benzyl group which may also have substituents, or -OR ^f , R ^f represents carbon number 1~ 20 straight, branched or cyclic alkyl groups, vinyl groups that may also have substituents, phenyl or benzyl groups that may also have substituents, or linked via alkylene groups with 1 to 4 carbon atoms ( Meth) acryloyl group, X represents a chlorine atom, a bromine atom, or an iodine atom; in the general formula (3), R ^c and R ^d each independently represent a hydrogen atom, a hydroxyl group, a straight chain with 1 to 20 carbon atoms, and a branch Chain or cyclic alkyl, vinyl, optionally substituted phenyl or benzyl, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons, A vinyl group, a phenyl group or a benzyl group which may also have a substituent, or a (meth)acryloyl group linked 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 second color material dispersion liquid for color filters of the present invention, which is used to solve the above-mentioned second object, is a color material dispersion liquid containing a color material, a dispersant, and a solvent; it is characterized by:

The above-mentioned color material contains C.I. Pigment Green 59;

The above-mentioned dispersant is a polymer having a structural unit represented by the following general formula (I);

[化2]

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

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

The color filter of the present invention has at least a transparent substrate and a coloring layer provided on the transparent substrate, and is characterized in that at least one of the colored layers has photosensitive coloring for the color filter of the present invention The colored layer formed by the hardening of the resin composition.

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

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

According to the first aspect of the present invention, it is possible to provide a color material dispersion liquid that is excellent in color material dispersion stability, suppresses the occurrence of development residues, and can produce a photosensitive color resin composition with excellent development adhesion and solvent resolubility; color material dispersion A photosensitive coloring resin composition for color filters that has excellent stability, suppresses the occurrence of development residues, has excellent development adhesion and solvent resolubility, and can form a coloring layer with excellent contrast; using this color filter for photosensitive A color filter formed by a colored resin composition; and a liquid crystal display device and an organic light-emitting display device with superior display characteristics by using the color filter.

Furthermore, according to the second invention, it is possible to provide a green color material dispersion that exhibits bluish green, excellent dispersion stability of the color material, and high brightness; using this color material dispersion, the solvent resolubility is excellent, and can be relied on. Brightness and high contrast, forming a coloring layer with excellent color reproducibility, a photosensitive colored resin composition for color filters; using this photosensitive colored resin composition for color filters has high brightness, high contrast and excellent color reproducibility Color filters; and liquid crystal display devices and organic light emitting display devices with high brightness and excellent color reproducibility by using the color filters.

1: Transparent substrate

2: Shading part

3: Coloring layer

10: Color filter

20: Opposite substrate

30: liquid crystal layer

40: Liquid crystal display device

50: Organic protective layer

60: Inorganic oxide film

71: Transparent anode

72: hole injection layer

73: Electric hole transport layer

74: luminescent layer

75: electron injection layer

76: cathode

80: organic light-emitting body

100: organic light emitting display device

Fig. 1 shows a schematic diagram of an example of the color filter of the present invention.

Fig. 2 shows a schematic diagram of an example of the liquid crystal display device of the present invention.

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

I. The first invention

Hereinafter, the color material dispersion liquid for color filters, the photosensitive colored 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.

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

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

In this specification, without special limitation, the chromaticity coordinates x and y are those of the XYZ color system of JIS Z8701 measured by the C light source.

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

The first color material dispersion liquid for color filters related to the present invention is a color material dispersion liquid containing a color material, a dispersant, and a solvent; it is characterized by:

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

P1: A block copolymer having an A block containing a structural unit represented by the following general formula (I) and a B block containing a structural unit derived from a carboxyl group-containing monomer;

P2: At least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) of the block copolymer is combined with the compound selected from the following general formulas (1) to (3) Salt type block copolymers of salts formed by more than one compound of the group of substances;

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

[化3]

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bonding group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, R ² and R ³ It can also be bonded to each other to form a ring structure;

In general formula (1), R ^a represents a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a phenyl group or a benzyl group which may also have a substituent, or a connection via an alkylene group with 1 to 4 carbons ( methyl) Bingxi Xi group; general formula 2) (, R ^b, R ^{b 'and} R ^{b "each} independently represent a hydrogen atom, an acidic group or an ester group, a substituent may also have a linear carbon number of 1 to 20 of the Chain, branched or cyclic alkyl group, vinyl group which may be substituted, phenyl group or benzyl group which may be substituted, or -OR ^f , R ^f represents carbon number 1 which may be substituted ~20 linear, branched or cyclic alkyl groups, vinyl groups which may also have substituents, phenyl or benzyl groups which may also have substituents, or linked via alkylene groups with 1 to 4 carbon atoms (Meth) allyl, X represents a chlorine atom, a bromine atom, or an iodine atom; in the general formula (3), R ^c and R ^d each independently represent a hydrogen atom, a hydroxyl group, a straight chain with 1 to 20 carbon atoms, Branched or cyclic alkyl, vinyl, optionally substituted phenyl or benzyl, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons , Vinyl, phenyl or benzyl which may also have substituents, or (meth)acrylic groups linked via alkylene groups with 1 to 4 carbon atoms; wherein at least one of ^{R c} and R ^{d contains carbon} atom.)

The color material dispersion of the present invention uses a block copolymer (P1) having the above-mentioned specific acid value and a specific glass transition temperature, containing the above-mentioned specific constituent unit, and a salt-type intercalation in which the block copolymer and the above-mentioned specific compound form a salt. At least one of the stage copolymers (P2) is used as a dispersant, so it is possible to produce a photosensitive colored resin composition that has excellent color material dispersion stability, suppresses the occurrence of development residues, and has excellent development adhesion and solvent resolubility. In addition, the photosensitive colored resin composition for color filters prepared by using the color material dispersion liquid can form a colored layer with excellent contrast.

By using a block copolymer (P1) having the above-mentioned specific acid value and a specific glass transition temperature, containing the above-mentioned specific structural unit, and a salt-type block copolymer (P2) in which the block copolymer and the above-mentioned specific compound form a salt At least one of) is used as a dispersant, and the function of exerting the above-mentioned effect is not clarified, but it can be estimated as follows.

Known as a pigment dispersant in the past, the dispersibility can be improved by having a block copolymer comprising an A block containing a specific repeating unit with an amine group or an ammonium salt group and a B block containing a repeating unit with an acidic group Or dispersion stability and alkali developability (for example, Patent Documents 1, 2 and 4).

However, after research by the inventors and others, according to the method described in Patent Document 1, in particular, the development density has not reached the practical level. According to the method described in Patent Document 1, as shown in the comparative example described later, it is estimated that the block copolymer contains a carboxylic acid The alcohol-derived part of the ester has a specific repeating unit of the alkylene oxide chain, so the glass transition temperature becomes lower. If the glass transition temperature of the block copolymer as the pigment dispersant is lower than or close to the temperature of the developer, the molecular motion of the dispersant during development increases, and as a result, it is estimated that the development adhesion is lowered.

In addition, in the methods described in Patent Documents 2 and 4, in particular, the developing adhesiveness is not up to a practical level. In the methods described in Patent Documents 2 and 4, as shown in the comparative examples described later, it is presumed that the cause is that the acid value of the dispersant is higher than the value specified in this case. Therefore, although the developability is superior, the polarity is too high and peeling is likely to occur. . In the methods described in Patent Documents 2 and 4, it is estimated that since the dispersant does not have the concept of satisfying a specific low acid value and a specific high glass transition temperature at the same time, the developing adhesiveness is not up to a practical level.

After intensive research, the inventors found that if the acid value of a specific block copolymer or salt-type block copolymer is higher, the developing viscosity cannot reach the practical level, and the solvent resolubility deteriorates; but if A low acid value below a specific value has the effect of suppressing development residues, can obtain good development adhesion that is not prone to peeling, and has excellent solvent resolubility. On the other hand, it was found that even if the specific block copolymer or salt-type block copolymer has a low acid value below the above-mentioned specific value, if the glass transition temperature is lower than the predetermined value, the developing tackiness does not reach the practical level; However, if a block copolymer or a salt type block copolymer having a glass transition temperature higher than the temperature of the developer by 30°C or more is used, the development adhesion is superior. If a block copolymer or salt-type block copolymer with a glass transition temperature higher than the temperature of the developer by 30°C or more is used, it is presumed that the reduction of development adhesion is suppressed by suppressing the molecular movement of the dispersant during development.

The color material dispersion liquid system related to the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention.

Hereinafter, each component of the color material dispersion liquid related to the present invention will be described in order starting from the characteristic dispersant in the present invention.

<Dispersant>

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

The structural unit represented by the above general formula (I) contained in the A block has basic properties and functions as a site for adsorbing color materials. In addition, when at least a part of the terminal nitrogen portion of the structural unit represented by the general formula (I) forms a salt with one or more compounds selected from the group consisting of the general formulas (1) to (3), the The salt forming part has a function as a part where the color material is more strongly adsorbed. On the other hand, the B block containing a structural unit derived from a carboxyl group-containing monomer has a function as a solvent-philic block. Therefore, the block copolymer system of the present invention shares the function of the A block adsorbed with the color material and the B block having solvent affinity, and exerts a function as a color material dispersant.

[Block copolymer]

{A block}

(Constitution unit shown in general formula (I))

In general formula (I), A is a direct bond or a divalent bond group. The so-called direct bonding means that A has no atoms, that is, C (carbon atom) and N (nitrogen atom) in general formula (I) are not bonded by other atoms.

Examples of the divalent bonding group in A include alkylene groups with 1 to 10 carbon atoms, Arylene group, -CONH- group, -COO- group, ether group with 1 to 10 carbon atoms (-R'-OR"-: R'and R" are independently alkylene groups) and combinations of these, etc. .

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.

In R ² and R ³ , the hydrocarbon group in the hydrocarbon group that may contain a hetero atom may be, for example, an alkyl group, an aralkyl group, an aryl group, and the like.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, isopropyl, tertiary butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc. The number of carbon atoms in the alkyl group is preferred. It is 1-18, more preferably methyl or ethyl.

As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, for example. The number of carbon atoms of the aralkyl group is preferably 7-20, more preferably 7-14.

Moreover, as an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group etc. are mentioned, for example. The number of carbon atoms of the aryl group is preferably 6-24, more preferably 6-12. In addition, the number of carbon atoms of the substituent is not included in the above-mentioned preferred number of carbon atoms.

The so-called heteroatom-containing hydrocarbon group refers to the above-mentioned hydrocarbon group having a structure in which carbon atoms are substituted by heteroatoms. Examples of the hetero atom that may be contained in the hydrocarbon group include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.

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

啉環等。 The term R ² and R ³ are bonded to each other to form a ring structure means that R ² and R ³ form a ring structure via a nitrogen atom. The ring structure formed by R ² and R ^{3 may also contain heteroatoms.} The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring,

Morpholino ring and so on.

啉環。 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, piperidine ring, or piperidine ring formed by bonding ^{R 2} and R ³

Morpholino ring.

Examples of the structural unit represented by the above general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and diethylamine (meth)acrylate (Meth)acrylic acid esters containing alkyl substituted amino groups such as diethylaminopropyl (meth)acrylate, etc., dimethylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, etc. (Meth)acrylamide containing alkyl substituted amino groups such as aminopropyl (meth)acrylamide, etc. Among them, from the viewpoint of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate are preferably used. Propyl (meth)acrylamide.

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

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

Within the scope of achieving the purpose of the invention, the A block may also have a structural unit other than the structural unit shown in the general formula (I), if it is a structural unit that can be copolymerized with the structural unit shown in the general formula (I) contain. For example, as a structural unit other than the structural unit shown in the general formula (I) that may be contained in the basic block portion, the "other structural unit" listed in the B block described later can be used, and specific examples include the general formula described later (II) The constituent units shown.

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

In addition, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is based on the viewpoint of good dispersibility and dispersion stability, relative to the total structural unit of the block copolymer The total mass is preferably 5-60% by mass, more preferably 10-50% by mass. In addition, the content ratio of each constituent unit in the block copolymer is calculated from the packing mass when the block copolymer before salt formation is synthesized.

Furthermore, the structural unit represented by the general formula (I) may have affinity with the color material, and may be composed of one type, or may contain two or more types of structural units.

{B block}

The B block is a block that does not contain the structural unit represented by the above general formula (I), but contains a structural unit derived from a carboxyl group-containing monomer. The B block is preferably selected from monomers that can be copolymerized with the structural unit represented by the general formula (I) and have unsaturated double bonds, and the solvent is appropriately selected according to the solvophilicity. use. As a standard, it is preferable to introduce the B block in such a way that the solubility of the copolymer at 23° C. becomes 20 (g/100g solvent) or more with respect to the solvent used in combination.

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

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

Examples of such monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, Gui Corticoic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride can also be used, ω -Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, as the precursor of the carboxyl group, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerization, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxyl group-containing monomer can be appropriately set so that the acid value of the block copolymer falls within the range of the above-mentioned specific acid value. It is limited, and it is preferably 0.05 to 4.5 mass%, more preferably 0.07 to 3.7% by mass relative to the total mass of the total constituent units of the block copolymer.

By setting the content ratio of the constituent unit derived from the carboxyl group-containing monomer to be above the above lower limit, the effect of suppressing development residues is excellent, and by being below the above upper limit, it is possible to prevent deterioration of development adhesion or solvent re-dissolution Sexual deterioration.

Furthermore, the structural unit derived from the carboxyl group-containing monomer should just have the above-mentioned specific acid value, and it may consist of one type, and may contain 2 or more types of structural units.

(Other constituent units)

In the B block, from the viewpoint of making the solvophilicity good, generally, in addition to the structural unit derived from the carboxyl group-containing monomer, it may further contain a structural unit that enhances the solvophilicity.

As the structural unit constituting the B block, for example, a monomer having an unsaturated double bond that can be copolymerized with a monomer derived from the structural unit represented by the general formula (I), of which the monomer of the general formula (II) is preferred. Indicates the constituent unit.

[化4]

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

The above-mentioned 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 general formula (II), A'can be the same as A in general formula (I). Among them, from the viewpoint of solubility in organic solvents, a direct bond, a -CONH- group, or a divalent bond group containing a -COO- group is preferred.

In 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.

基、異

基、二環戊基、二環戊烯基、金剛烷基、低級烷基取代金剛烷基等。 The above-mentioned alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethyl Hexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl,

Base, different

Group, dicyclopentyl, dicyclopentenyl, adamantyl, lower alkyl substituted adamantyl, etc.

The above-mentioned alkenyl group with 2 to 18 carbon atoms can be linear, branched, or cyclic. One. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group, etc. are mentioned, for example. The position of the double bond of the alkenyl group is not limited. From the viewpoint of the reactivity of the obtained polymer, it is preferably one having a double bond at the end of the alkenyl group.

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

As an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aryl group is preferably 6-24, more preferably 6-12.

Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group etc. are mentioned, for example, and it may have a substituent further. The number of carbon atoms of the aralkyl group is preferably 7-20, more preferably 7-14.

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

Furthermore, the above-mentioned 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 from 1 to 18, preferably an integer from 1 to 4, more preferably an integer from 1 to 2; y is an integer from 1 to 5, preferably an integer from 1 to 4, more preferably It is 2 or 3. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.

The hydrocarbon group in the above R ⁸ can be the same as that shown in the ^{above R 5.}

R ⁹ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, which may be linear, branched, or cyclic.

^{In addition, R 5} in the structural unit represented by the above general formula (II) may be the same or different from each other.

As the above-mentioned R ⁵ , it is preferable to select one having excellent compatibility with the solvent described below. Specifically, for example, a glycol ether generally used as a solvent for a colored resin composition for a color filter is used in the above-mentioned solvent In the case of solvents such as acetate-based, ether-based, and ester-based solvents, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, and the like are preferred.

Furthermore, the above-mentioned R ⁵ may be substituted with a substituent such as alkoxy, hydroxyl, epoxy, isocyanate, etc., within a range that does not hinder the dispersibility of the above-mentioned block copolymer, or may be substituted in the above-mentioned After the block copolymer is synthesized, it is reacted with the compound having the above-mentioned substituent to add the above-mentioned substituent.

The number of the constituent units constituting the B block is not particularly limited. From the viewpoint of effective action of the solvent-philic part and the color-philic material part to improve the dispersibility of the color material, it is preferably 10 to 300, more preferably 10 ~100 pcs, better 10~70 pcs.

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

In addition, in the block copolymer before salt formation, the content ratio of the constituent units represented by the above general formula (II) is based on the viewpoint of improving the dispersibility of the color material, relative to the total mass of the total constituent units of the block copolymer , Preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content ratio of the above-mentioned structural unit is calculated from the packing mass during synthesis of the block copolymer before salt formation.

The structural unit of the B block may be appropriately selected so as to function as a solvophilic part. The structural unit represented by the above general formula (II) may be composed of one type, or may contain two or more types of structural units. Two or more structural units contained in the B block may also be randomly arranged in the block.

In the present invention, the B block of the block copolymer preferably contains a structural unit derived from a hydroxyl group-containing monomer from the viewpoint of improving the development adhesion. In the case of containing a structural unit derived from a hydroxyl-containing monomer, it is believed to improve the development adhesion due to the easy interaction with glass or metal commonly used as a substrate. In the B block, when a structural unit derived from a hydroxyl-containing monomer is contained, the development speed is further improved.

Furthermore, the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

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

From the viewpoint of improving the developability, those having a first-level hydroxyl group are better than those having a second-level hydroxyl group. In addition, the first-order hydroxyl group refers to a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a first-order carbon atom; and the second-order hydroxyl group refers to a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a second-order carbon atom.

As will be described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or higher. From the viewpoint of improving the development adhesion, it is preferable to use the glass transition temperature of the homopolymer of each monomer. A hydroxyl-containing monomer having a value (Tgi) of 0°C or higher, more preferably a hydroxyl-containing monomer having a value of 10°C or higher.

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

In addition, in the block copolymer (P1) before salt formation, the content ratio of the constituent units derived from the hydroxyl-containing monomer is relative to the total mass of the total constituent units of the block copolymer, and is preferably 1% by mass or more, More preferably 2% by mass or more, still more preferably 3% by mass or more, particularly preferably 4% by mass or more. If it is more than the above lower limit, it can be made with better developing adhesion. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass or less. If it is below the above upper limit, it can be made better from the viewpoint of increasing the introduction ratio of other useful monomers. In addition, the content ratio of the above-mentioned structural unit is calculated from the packing mass at the time of synthesis of the block copolymer before salt formation.

Furthermore, in the present invention, the B block preferably contains a structural unit derived from an aromatic group-containing monomer from the viewpoint of improving solvent resolubility. In the case of containing a structural unit derived from an aromatic group-containing monomer, since it is easy to improve the compatibility with the solvent or other components, it is considered that the solvent re-solubility can be improved.

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

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

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

In addition, in the block copolymer (P1) before salt formation, the content ratio of the constituent units derived from the aromatic group-containing monomer is relative to the total constituent units of the block copolymer from the viewpoint of improving solvent resolubility The total mass of is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, particularly preferably 4% by mass or more. If it is more than the above lower limit, it can be made into a solvent with better 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, particularly preferably 40% by mass or less. If it is below the above upper limit, it can be made better from the viewpoint of increasing the introduction ratio of other useful monomers.

In addition, among them, the B block having a solvophilic property preferably contains (i) a structural unit derived from a hydroxyl-containing monomer and an aromatic group-containing unit from the viewpoint of improving the developing adhesion and solvent resolubility. The constituent unit of the monomer; and (ii) at least one of the constituent units derived from the carboxyl group and aromatic group-containing monomer.

In the case of containing (i) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer, relative to 1 part by mass of the structural unit derived from the aromatic group-containing monomer, it is preferable to contain The constitutional unit of the hydroxyl monomer is 0.15 parts by mass or more, and more preferably contains 0.5 parts by mass or more. If it is more than the above lower limit, it can be made into a product with superior developing adhesion. Also, in the same way, it is preferable to contain 15 parts by mass or less, more preferably 7 parts by mass or less of the constituent unit derived from the hydroxyl-containing monomer with respect to 1 part by mass of the constituent unit derived from the aromatic group-containing monomer. If it is less than the above upper limit, it can be made into a solvent with excellent resolubility. Among them, it is particularly preferred that the value of the glass transition temperature (Tgi) relative to the homopolymer is 1 part by mass 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 within the above range. Value (Tgi) becomes 10 It is a constituent unit derived from a hydroxyl-containing monomer at a temperature above °C. By containing each component above the above lower limit value, it can be made to have more superior developing adhesion, and by containing each component below the above upper limit value, it can be made into a product with superior solvent solubility.

In addition, (ii) monomers containing a hydroxyl group and an aromatic group in the structural unit derived from a monomer containing a hydroxyl group and an aromatic group include, for example, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2 -Acrylic oxyethyl-2-hydroxyethyl-phthalic acid and the like. The value of the glass transition temperature (Tgi) of the homopolymer of 2-hydroxy-3-phenoxypropyl (meth)acrylate is 10°C or more, and the effect obtained from the structural unit derived from the hydroxyl-containing monomer can be obtained. From the viewpoint of any one of the effects derived from the structural unit of the aromatic group-containing monomer, it is more suitable for use. That is, it is preferable from the viewpoint of improving the development adhesion, the development speed, and the solvent resolubility.

(ii) In the case of containing structural units derived from monomers containing hydroxyl and aromatic groups, since one structural unit can improve development adhesion, development speed, and solvent resolubility, it also has other functions that can be improved Advantages of the introduction ratio of sexual monomers.

In addition, as described later, the glass transition temperature of the dispersant used in the present invention is set to a specific value or higher. From the viewpoint of improving the development adhesion, it is preferable to set the glass transition temperature of the homopolymer of the monomer to be lower than the glass transition temperature of the homopolymer. For monomers having a value (Tgi) of 10°C or higher, the total content in the B block is 75% by mass or more, more preferably 85% by mass or more.

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

In addition, the amine value of the block copolymer (P1) before salt formation is not particularly limited, but from the viewpoint of color material dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 60 mgKOH/g or more. Furthermore, the upper limit is preferably 140 mgKOH/g or less, more preferably 130 mgKOH/g or less, and still more preferably 120 mgKOH/g or less. If it is more than the above lower limit, the dispersion stability is more excellent. Moreover, if it is less than the said upper limit, the compatibility with other components will be excellent, and the solvent re-solubility will become favorable.

Furthermore, in the present invention, the so-called amine valence of the block copolymer before salt formation refers to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the block copolymer before salt formation, to become the equivalent of hydroxide The mass (mg) of potassium is expressed as a value measured by the method described in JIS K 7237.

The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited. From the viewpoint of good color material dispersibility and dispersion stability, it is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 3,000 to 12,000. .

Here, the weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC), as a standard polystyrene conversion value.

Furthermore, in the present invention, the weight average molecular weight Mw of the block copolymer is determined by GPC (gel permeation chromatography) as a standard polystyrene conversion value. Tosoh Corporation’s HLC-8120GPC was used for the measurement, and the elution solvent was N-methylpyrrolidone added with 0.01 mol/liter of lithium bromide, and the polystyrene standard for the calibration curve was set to Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (The above are Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Co., Ltd.), set the measuring column to TSK-GEL ALPHA-MX2 (Tosoh Corporation). In addition, the macromonomers, salt-type block copolymers, and graft copolymers used as raw materials for the block copolymers are carried out under the above-mentioned conditions.

In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and it can be, for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like. Among them, from the viewpoint of superior dispersibility, AB block copolymers or ABA block copolymers are preferred.

The method for producing the block copolymer is not particularly limited, and the block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method. This is due to the fact that chain movement or deactivation is not prone to occur, copolymers with the same molecular weight can be produced, and dispersibility can be improved. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization methods and radical transfer polymerization methods, living cationic polymerization methods, and the like. By sequentially polymerizing monomers by such methods, copolymers can be produced. For example, the A block is first produced, and the A block is polymerized with the constituent units constituting the B block to produce a block copolymer. In addition, in the above-mentioned production method, the order of polymerization of the A block and the B block may be reversed. In addition, the A block and the B block may be produced separately, and then the A block and the B block may be coupled.

[Salt type block copolymer]

In the present invention, it is also possible to use at least a part of the terminal nitrogen portion of the structural unit represented by the general formula (I) of the block copolymer, and a compound selected from the group of compounds represented by the general formula (1) to (3). A salt-type block copolymer of salts formed by one or more compounds in the group.

The above-mentioned salt-type block copolymer is more suitable for use with respect to the salt formation site in the structural unit represented by the above general formula (I), from the viewpoint of further improving the color material adsorption and the color material dispersibility.

(Choose more than one compound from the group of compounds represented by the above general formulas (1) to (3))

The aforementioned general formula (1) to (3), the carbon number as ^{R a, R b, R b} ', R b ", R c, R d, R e , and in R ^f of the linear-chain having 1 to 20, the points The branched or cyclic alkyl group may be either linear or branched, or may contain a cyclic structure. Specific examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Base, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, dodecyl, Cyclopentyl, cyclohexyl, tetradecyl, octadecyl, etc. Preferred examples include linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, and more preferably examples of carbon number 1. ~8 linear, branched or cyclic alkyl.

^{And, R a, R c, R} d and R ^e, as the substituted group may have a substituent group of the phenyl or benzyl group, and may be for example carbon atoms, such as 1 to 5 of the alkyl, acyl, acyl oxygen Base and so on.

Among R ^b , R ^b' , R ^b" and R ^f , examples of the substituent of the phenyl or 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. , Acyl group, acyloxy group, etc.

In addition, among R ^b , R ^b' , R ^b" and R ^f , as a substituent of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a vinyl group, which may have a substituent, For example, an acidic group or its ester group, a phenyl group, an acyl group, an acyloxy group, etc. are mentioned.

In R ^b , R ^b' , R ^b" and R ^f , the so-called acidic group refers to a group that releases protons in water to show acidity. Specific examples of acidic groups include carboxyl (-COOH), sulfonic acid Group (-SO ₃ H), phosphinyl group (-P(=O)(OH) ₂ ), phosphonic acid subunit (>P(=O)(OH)), boronic acid group (-B(OH) ₂ ) , Ci-yl boronic acid (> BOH) and the like, such as carboxymethylcellulose may also be the foundation (-COO ^-) and the like generally have a hydrogen atom from the anion solution, and thus may also be formed a salt with the alkali metal ions such as sodium or potassium ions or the like acid salt .

Moreover, as the ester group of the acidic group, for example, carboxylate (-COOR), phosphate (-SO ₃ R), phosphate (-P(=O)(OR) ₂ ), phosphonic acid subunit (> P(=O)(OR)), borate (-B(OR) ₂ ), hypoborate (>BOR), etc. Among them, the ester group of the acidic group is preferably a carboxylic acid ester (-COOR) from the viewpoint of dispersibility and dispersion stability. In addition, 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), from the viewpoints of dispersibility, dispersion stability, alkali developability, and development residue suppression, preferably has an anion selected from the group consisting of carboxyl group, boronic acid group, boronic acid group, and the like , And these alkali metal salts, and one or more functional groups of these esters, among them, it is more preferable to have a functional group selected from a carboxyl group, a carboxyl group, a carboxylate group, and a carboxylate.

In the case where the compound of the above general formula (2) has an acidic group and its ester group (hereinafter referred to as acidic group etc.), either the acidic group or the like and the halogen atom-side hydrocarbon possessed by the compound may interact with the terminal The nitrogen site forms a salt. Compared to the case where the terminal nitrogen site forms a salt with an acidic group, it is estimated that the terminal nitrogen site and the halogen atom side hydrocarbon can stably form a salt. Furthermore, it is presumed that the dispersibility and dispersion stability can be improved if the color material is adsorbed by the stably existing salt formation site.

When the compound of the aforementioned general formula (2) has the aforementioned acidic group or the like, it may have two or more of the aforementioned acidic group or the like. In the case of having two or more acidic groups, etc., the plurality of acidic groups may be the same or different. The number of the acidic groups and the like possessed by the compound of the general formula (2) is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

At least one of R ^a in the above general formula (1), R ^b , R ^b'and R ^{b" in} the above general formula (2), and at least one ^{of R c and Rd in the above general formula (3) have} In the case of an aromatic ring, the affinity with the skeleton of the color material described later can be improved, and the dispersion and dispersion stability of the color material are superior, and a coloring composition with superior contrast can be obtained, so it 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, mono-n-propylsulfuric acid, and the like. In addition, hydrates like p-toluenesulfonic acid monohydrate can also be used. As the compound represented by the above general formula (2), for example, methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, Hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, benzyl iodide , Chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-iodophenylbenzoic acid, chlorine Acetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenyl acetate, 3-(bromomethyl)phenylboronic acid, etc. As the compound represented by the above general formula (3), for example, monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenyl phosphinic acid, phenyl phosphoric acid, dimethyl phosphoric acid, Acrylic acid oxyethyl phosphoric acid and the like.

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

In addition, from the viewpoint of superior dispersion stability and improved suppression of development residues by combining with the block copolymer (P1) having an acid value, it is also suitable to use acidic Group and its ester group represented by the general formula (2), among them, it is also suitable to use selected from α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid , 4-bromomethyl benzoic acid, and 4-iodophenyl benzoic 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 fact that the content of the terminal nitrogen part of the structural unit represented by the general formula (I) A salt is formed, so one or more compounds selected from the group consisting of the above general formulas (1) to (3) are set to 1 mol relative to the terminal nitrogen site of the structural unit represented by the general formula (I) 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.2 mol or more, particularly preferably 0.3 mol or more. If it is more than the above lower limit, the effect of improving the dispersibility of the color material due to salt formation is easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.7 mol or less, particularly preferably 0.6 mol or less. If it is less than the above upper limit, it can be made into a product with superior developing adhesion or solvent resolubility.

Furthermore, one or more compounds selected from the group consisting of the above 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 is preferably within the above-mentioned range.

As a method for preparing the salt-type block copolymer, for example, adding one or more compounds selected from the group consisting of the above general formulas (1) to (3) in a solvent in which the block copolymer is dissolved or dispersed. And stirring, and then heating method as necessary.

Moreover, the terminal nitrogen site of the structural unit represented by the general formula (I) of the block copolymer forms a salt with one or more compounds selected from the group consisting of the general formulas (1) to (3) above The situation and its ratio can be confirmed by known methods such as NMR.

The amine valence of the salt block copolymer (P2) obtained is only higher than that before the salt formation The block copolymer (P1) forms a small value of the amount of salt. However, since the salt formation site becomes the same or stronger color material adsorption site as the nitrogen site at the end equivalent to the amine group, the salt formation tends to improve the color material dispersibility or the color material dispersion stability. In addition, the salt formation site is the same as the amine group, and if it is too large, it will adversely affect the solvent resolubility. Therefore, in the present invention, the amine value of the block copolymer (P1) before salt formation can be used as an index for improving the 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.

If it is less than the above upper limit, the compatibility with other components is excellent, and the solvent resolubility is good.

Furthermore, in the salt-type block copolymer (P2), the amine value of the salt-type block copolymer formed by the compound represented by the above general formula (2) as a salt can be determined by the method described in JIS K 7237 value. In the compound of the above general formula (2), since the terminal nitrogen part of the structural unit represented by the general formula (I) forms a salt with the halogen atom side hydrocarbon, even by this measurement method, the salt-formed State, so the amine value can be measured.

On the other hand, in the salt-type block copolymer (P2), the amine valence of the salt-type block copolymer in which a salt is formed by the compound represented by the above general formula (1) or (3) is determined from the value before the salt is formed. The amine value of the block copolymer is calculated as follows. In the compound represented by the above general formula (1) or (3), since the terminal nitrogen site of the constituent unit represented by the general formula (I) forms a salt with an acidic group, it is determined by the method described in the above 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, by the above method, the amine of the block copolymer (P1) before salt formation price. Next, the 13C-NMR spectrum of the salt-type block copolymer was measured using a nuclear magnetic resonance device. In the obtained spectrum data, the nitrogen site at the end of the constituent unit represented by the above general formula (I) was combined with the unformed salt The ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom and the peak of the carbon atom adjacent to the nitrogen atom forming the salt is measured, and the ratio of the salt-type block copolymer is measured relative to the structural unit shown in the general formula (I) The nitrogen site at the end is selected from the reaction rate of one or more compounds in the group consisting of the above general formula (1) or (3) (the rate of the nitrogen site at the end forming the salt). One or more compounds selected from the group consisting of the above general formula (1) or (3) form a salt at the terminal nitrogen portion of the structural unit represented by the general formula (I), and the amine value is set to 0, By (the amine value of the salt-forming pre-block copolymer (P1) measured by the method described in JIS K 7237) × (the ratio of the nitrogen site at the end of the formed salt calculated from the 13C-NMR spectrum (%)/100 ) Is calculated by subtracting the amine value consumed by salt formation from the amine value of the block copolymer before salt formation.

The amine value of the salt-type block copolymer (P2) = {The amine value of the salt-formed block copolymer (P1) measured by the method described in JIS K 7237}-{Measured by the method described in JIS K 7237 The amine value of the block copolymer (P1) before the formation of the salt)×{The ratio of the nitrogen site at the end of the formed salt calculated from the 13C-NMR spectrum (%)/100}

The lower limit of the acid value of the dispersant used in the present invention is 1 mgKOH/g or more from the viewpoint of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH/g or more from the viewpoint that the effect of suppressing the development residue is more superior. In addition, the upper limit of the acid value of the dispersant used in the present invention is 18 mgKOH/g or less from the viewpoint of preventing the deterioration of developing adhesion or the deterioration of solvent resolubility. Among them, the acid value of the dispersant is more preferably 16 mgKOH/g or less, and even more preferably 14 mgKOH/g or less, from the viewpoint of good developing adhesion and solvent resolubility.

In the dispersant used in the present invention, the acid of the block copolymer (P1) before the salt is formed The valence is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. This is because the suppression effect of developing residue can be improved. 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, and more preferably 14 mgKOH/g or less. This is to make the developing adhesion and solvent re-solubility good.

As mentioned above, the acid value of the block copolymer (P1) before salt formation is based on the mass (mg) of potassium hydroxide required to neutralize the acidic components contained in 1g of the solid content of the block copolymer. It is the value measured by the method described in JIS K 0070.

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

On the other hand, when the salt-type block copolymer (P2) is a salt-type block copolymer in which a salt is formed by the compound represented by the above general formula (1) or (3), the acidic base system used for the salt formation Remove and calculate the acid value. This is because the acidic group used for salt formation does not function as an acidic group that increases the acid value of the dispersant. Therefore, in this case, the acid value of the salt-type block copolymer formed by the compound represented by the above general formula (1) or (3) is calculated based on the value obtained by the following formula. This is because if the acid value of the salt type block copolymer formed by the compound represented by the general formula (1) or (3) is measured by the method described in the above JIS K 0070, the state of the salt formation will change. , Cannot determine the correct value.

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

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

The acid value consumed due to salt formation, specifically, for example, using a nuclear magnetic resonance device to measure the 13C-NMR spectrum of the salt-type block copolymer. The ratio of the integral value of the peak of the carbon atom adjacent to the atom and the peak of the carbon atom adjacent to the nitrogen atom forming the salt is calculated, and the ratio of the number of nitrogen sites at the end of the salt formed to the total number of nitrogen sites at the end is calculated. According to {the amine value of the salt-forming pre-block copolymer (P1) measured by the method described in JIS K 7237}×{calculated by 13C-NMR spectrum of the nitrogen site ratio at the end of the formed salt (%)/100 }, calculate the amine value consumed, which is the same value as the acid value consumed due to salt formation.

However, when the compound represented by the above general formula (1) is formed into a salt less than 1 mol with respect to 1 mol of the terminal nitrogen site of the structural unit represented by the general formula (I), the When the compound represented by the above general formula (3) with an acidic group forms a salt with 1 mol or less, or when the compound represented by the above general formula (3) with 2 acidic groups is formed as a salt with 0.5 mol or less, the acid If the total amount of the group forms a salt with the terminal nitrogen site of the constituent unit represented by the general formula (I), in the salt-type block copolymer after the salt is formed, the acidic group does not affect the acid value, so 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) with two acidic groups is added at a molar number exceeding the above-mentioned number of moles, after the salt is formed, there are acidic groups that do not form a salt in the dispersant. Therefore, as mentioned above, the acid that does not form the acidic group of the salt The value is added to the acid value of the block copolymer before the salt is formed, and the acid value of the dispersant is calculated.

Furthermore, in the present invention, the glass transition temperature of the dispersant is 30°C or higher. That is, whether the dispersant is a block copolymer (P1) or a salt type block copolymer (P2), its glass transition temperature is 30°C or higher.

When the glass transition temperature of the dispersant is less than 30°C, especially if the temperature of the developer solution (usually around 23°C) is equal to or lower, the development adhesion will decrease. This is because if the glass transition temperature is equal to or lower than the temperature of the developer, the movement of the dispersant during development becomes larger, and as a result, it is estimated that the development density is deteriorated.

The glass transition temperature of the dispersant is preferably 32°C or higher, and more preferably 35°C or higher from the viewpoint of developing adhesion. On the other hand, from the viewpoint of operability at the time of use, such as ease of a precision scale, it is preferably 200°C or lower.

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

Among them, the glass transition temperature (Tg) of the block copolymer without salt formation is calculated according to the following formula, which can be used as an index.

1/Tg=Σ(Xi×Tgi)

Here, the block copolymerization system is assumed to copolymerize n monomer components up to i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, the Σ system uses the sum from i=1 to n. Moreover, the value of the glass transition temperature (Tgi) of the homopolymer of each monomer can be the value of the Polymer Handbook (3rd Edition) (J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

The glass transition temperature obtained from this calculated value is as shown in the following examples. Since it is almost the same value as the above-mentioned measured value obtained by DSC, it can be regarded as an unformed An indicator of the glass transition temperature of salt block copolymers.

In the color material dispersion of the present invention, as a dispersant, at least one of the above-mentioned block copolymers and salt-type block copolymers is used, and its content is based on the type of color material used, and the color filter described later The solid content concentration in the photosensitive colored resin composition for sheets, etc., is appropriately selected.

The content of the dispersant is relative to 100 parts by mass of the total solid content in the color material dispersion, preferably 3~45 parts by mass, preferably 5~35 parts by mass. If it is more than the above lower limit, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive colored resin composition for color filters is even more excellent. Moreover, if it is less than the said upper limit, developability will become favorable.

Especially in the case of forming a coating film or colored layer with a high color material concentration, the content of the dispersant is relative to the total solid content of the color material dispersion 100 parts by mass, preferably 3-25 parts by mass, more preferably 5 parts by mass ~20 parts by mass.

Furthermore, in the present invention, the solid content is an owner other than the above-mentioned solvent, and includes monomers dissolved in the solvent, and the like.

<color material>

In the present invention, the color material is only one that can emit the desired color when forming the coloring layer of the color filter. The rest is not particularly limited. Various organic pigments, inorganic pigments, and dispersible dyes can be used alone or in combination. Used above. Among them, organic pigments have high color development and high heat resistance, so they are suitable for use. Examples of organic pigments include compounds classified as pigments in the color index (C.I.; issued by The Society of Dyers and Colourists), and specific examples include those with the following color 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 CI Pigment Yellow 150 derivative pigments;

C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;

C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;

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;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;

C.I. Pigment Green 7, 36, 58, 59;

C.I. Pigment Brown 23, 25;

C.I. Pigment Black 1,7.

Among them, as the color material, when C.I. Pigment Green 59 is contained, it is preferable from the viewpoint that a green color material dispersion liquid exhibiting bluish green, excellent color material dispersion stability, and high brightness can be obtained. If the green color material dispersion is used, the color filter The green pixels of the film do not need to be thickened, and the above-mentioned high-density green chromaticity area can be made, and high brightness or high contrast can be achieved. The C.I. Pigment Green 59 will be described in detail in the second description of the present invention described later. In addition, the derivative pigment of C.I. Pigment Yellow 150 will also be described in detail in the second description of the present invention described later.

In addition, specific examples of the above-mentioned inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, Bengal (Bengala, red iron oxide (III)), cadmium red, and ultramarine blue. , Cyan, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, etc.

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

As the above-mentioned dispersible dyes, for example, various substituents can be given to the dyes, or a well-known lakeing (salting) technique can be used to insolubilize a solvent to become a dispersible dye, or a combination of low-solubility dyes can be used. The solvent becomes a dispersible dye. By using this dispersible dye in combination with the above-mentioned dispersant, the dispersibility or dispersion stability of the dye can be improved.

染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 As the dispersible dye, it can be appropriately selected from conventional dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes,

Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc.

Moreover, as a standard, if the dissolved amount of the dye is 10 mg or less relative to 10 g of the solvent (or mixed solvent), it can be judged that the dye is in the solvent (or mixed solvent) Can be dispersed.

As the average primary particle size of the color material used in the present invention, in the case of forming the coloring layer of the color filter, it is not particularly limited as long as it can emit the desired color, although it depends on the color material used It varies depending on the kind, but it is preferably in the range of 10 to 100 nm, more preferably 15 to 60 nm. By setting the average primary particle size of the color material within the above range, a display device equipped with a color filter manufactured using the color material dispersion liquid of the present invention can be of high contrast and high quality.

Furthermore, the average primary particle size of the color material of the present invention is represented by "volume distribution median diameter (D50)". The average primary particle size of the color material is manufactured by Hitachi High Technologies Co., Ltd., a field emission scanning electron microscope (S-4800), equipped with a dedicated bright-field STEM stage and selective detector, so that it can be used for scanning Transmission electron microscope (hereinafter referred to as "STEM"), take 200,000 times STEM photos, read them into the following software, select 100 color materials on the photos, and measure their diameters (diameter length). The standard distribution is calculated as 50% cumulative particle size based on volume.

The measurement sample for STEM is prepared by mixing the color material and toluene, dripping it onto the collodion film and attaching the net. In addition, when obtaining the volume-based particle size distribution or the volume distribution median diameter (D50) from the STEM photograph, the image analysis type particle size distribution measurement software "Mac-View Ver. 4" manufactured by Mountech Co., Ltd. was used.

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

The average dispersed particle diameter of the color material in the color material dispersion is the dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, measured by a laser light scattering particle size distribution meter. As the particle size measurement carried out by the laser light scattering particle size distribution meter, it is based on the color Dilute the color material dispersion to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times, etc.) using the solvent used in the material dispersion liquid. Use a laser light scattering particle size distribution meter (such as NANOTRACK manufactured by Nikkiso The particle size distribution measuring device UPA-EX150) was measured at 23°C by the dynamic light scattering method. The average distribution particle size here is the volume average particle size.

The color material used in the present invention can be produced by a known method such as a recrystallization method and a solvent salt grinding method. In addition, commercially available color materials can also be used by subjecting them to finer processing.

The content of the color material in the color material dispersion of the present invention is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of color material is preferably 5 to 80 parts by mass, more preferably 8 to 70 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. Deployment.

Especially in the case of forming a coating film or colored layer with a high color material concentration, relative to the total solid content in the color material dispersion 100 parts by mass, preferably 30 to 80 parts by mass, more preferably 40 to 75 parts by mass Proportional deployment.

<Solvent>

The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with the respective components in the color material dispersion liquid and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.

Specific examples of solvents include alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxyethanol Carbitol solvents such as 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, Ester solvents such as ethyl lactate and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.; methoxy ethyl Acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate Glycol ether acetate solvents such as esters; carbitol such as methoxy ethoxy ethyl acetate, ethoxy ethoxy ethyl acetate, butyl carbitol acetate (BCA), etc. Alcohol acetate solvents; diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether , Diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether and other glycol ether solvents; N,N-dimethyl methyl ether Non-protonic amide solvents such as amines, N,N-dimethylacetamide and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; cyclic ether-based solvents such as tetrahydrofuran; Unsaturated hydrocarbon solvents such as benzene, toluene, xylene, naphthalene, etc.; saturated hydrocarbon solvents such as N-heptane, N-hexane, N-octane, etc.; organic solvents such as aromatic hydrocarbons such as toluene and xylene Solvent. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used from the viewpoint of the 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 viewpoint of solubility of other components or coating suitability. Ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate More than one kind.

The color material dispersion of the present invention, relative to the total amount of the color material dispersion containing the solvent, usually preferably contains the above solvent in the range of 55-95% by mass, and preferably in the range of 65-90% by mass , Better within the range of 70~88% by mass. If the solvent is too small, the viscosity will increase and the dispersibility will tend to decrease. In addition, if the solvent is too much, the concentration of the colored material will decrease, making it difficult to achieve the target chromaticity coordinates.

<Other ingredients>

In the color material dispersion of the present invention, without impairing the effect of the present invention, a dispersion auxiliary resin and other components can be further formulated as needed.

Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the photosensitive colored resin composition for color filters described below. Because of the steric obstacle of the alkali-soluble resin, the color material particles are not easily contacted with each other, and there are cases where the dispersion stabilization or the dispersion stabilization effect reduces the effect of the dispersant.

In addition, as other components, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, defoaming agents, shrinkage inhibitors, antioxidants, anti-aggregating agents, ultraviolet absorbers, etc. .

The color material dispersion of the present invention is used as a preliminary preparation for preparing a photosensitive colored resin composition for color filters described later. In other words, the so-called color material dispersion is prepared in the stage prior to the preparation of the photosensitive colored resin composition for color filters described below, (the mass of the color material in the composition)/(the color material in the composition other than the color material in the composition) The solid content mass) relatively high color material dispersion liquid. Specifically, the ratio of (mass of color material components in the composition)/(mass of solids other than the color material components in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid with the components described below, a photosensitive colored resin composition for color filters with excellent dispersibility can be prepared.

<Method for manufacturing color material dispersion>

In the present invention, if 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 color material as a dispersant for the block copolymer or salt type block copolymer, There is no particular limitation. Among them, the dispersion and dispersion of color materials From the viewpoint of excellent stability, it is preferable to use any of the following two production methods.

That is, the first production method of the color material dispersion of the present invention includes the steps of preparing a dispersant for the above-mentioned block copolymer or salt-type block copolymer; and in a solvent, in the presence of the above-mentioned dispersant , The step of dispersing the color material.

In addition, in the case of using a dispersant belonging to the salt-type block copolymer, the second method for producing the color material dispersion of the present invention includes: a solvent, the block copolymer, and the above general formula (1)~ (3) One or more compounds in the group are mixed with a color material, and at least a part of the terminal nitrogen site of the constituent unit represented by the above general formula (I) forms a salt with the above compound. The step of material dispersion.

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

In addition, according to the second production method described above, the color material is dispersed under the dispersant of the salt-type block copolymer. Therefore, the salt-type block copolymer does not self-aggregate, and the color material dispersion can be prepared efficiently. And can improve the dispersion.

In the above-mentioned first manufacturing method and the above-mentioned second manufacturing method, the color material can be dispersed using a conventional dispersing machine.

Specific examples of the dispersing machine include roller mills such as two-roll mills and three-roll mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, continuous disc type bead mills, continuous ring type bead mills, etc. Mill. For the better dispersion conditions of the bead mill, the diameter of the grinding beads used is preferably 0.03~3.0mm, more preferably 0.05~2.0mm.

Specifically, for example, first use the 2.0mm diameter of the grinding bead with a larger diameter. The zirconia balls are pre-dispersed, and then the 0.1mm zirconia balls with a smaller grinding bead diameter are used for formal dispersion. Furthermore, after dispersion, it is preferable to filter with a membrane filter of 0.5 to 2 μm.

I-2. The first photosensitive colored resin composition for color filters of the present invention

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

The first photosensitive colored resin composition for color filters of the present invention, by using the above-described first color material dispersion liquid related to the present invention, has excellent color material dispersion stability, suppresses the occurrence of development residues, and simultaneously develops It has excellent image density and solvent re-solubility; in addition, it can form a coloring layer with excellent contrast.

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, which does not impair the effect of the present invention. Within the range, other components may be further contained. Hereinafter, the components contained in the photosensitive colored resin composition for color filters of the present invention will be described. However, since the dispersant, color material, and solvent are all the same as those described in the above-mentioned color material dispersion liquid 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 the developer used in pattern formation, particularly preferably one that is soluble in alkaline developer, can be appropriately selected and used.

The preferred alkali-soluble resin in the present invention is a tree having a carboxyl group as an acidic group Specific examples of the grease include acrylic copolymers having carboxyl groups, styrene-acrylic copolymers having carboxyl groups, epoxy (meth)acrylate resins having carboxyl groups, and the like. Among these, particularly preferable ones are those having a carboxyl group in the side chain, and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. The reason is that by containing a photopolymerizable functional group, the film strength of the formed cured film can be improved. In addition, these acrylic copolymers, styrene-acrylic copolymers, and epoxy acrylate resins can also be used in combination of two or more.

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

Specific examples of acrylic copolymers having a carboxyl group include those described in Japanese Patent Laid-Open No. 2013-029832, and specific examples include: methyl (meth)acrylate, ethyl (meth)acrylate, etc. A monomer that does not have a carboxyl group and a copolymer composed of one or more selected from (meth)acrylic acid and its acid anhydride. In addition, it is also possible to exemplify the addition of ethylenically unsaturated compounds having reactive functional groups such as glycidyl and hydroxyl groups to the above-mentioned copolymers, and polymers with ethylenically unsaturated bonds introduced, but are not limited to And so on.

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

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is usually 5-50% by mass, preferably 10-40% by mass. In this case, if the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film in an alkaline developer is reduced, and pattern formation is difficult. Also, if the copolymerization ratio For example, if it exceeds 50% by mass, when developing with an 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 performance of the adhesive after curing is significantly reduced, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer.

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

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

Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known materials for use.

As an epoxy (meth)acrylate resin having a carboxyl group, a structure (carbodole structure) in which two benzene rings are bonded to the pyrene skeleton represented by the following chemical formula (A) is contained in the molecule, and the display is improved It is preferable from a viewpoint of a poor suppression effect, and the hardenability of a colored layer is improved, or the residual film rate of a colored layer becomes high.

[化5]

Epoxy (meth)propylene with carboxyl group containing the above-mentioned carbodole structure The exact mechanism of the acid ester resin (hereinafter referred to as the carbodole resin) has not been elucidated, but it is considered that since the 茀 frame contains a π-conjugated system, it is highly sensitive to free radicals. Dole resin can improve the required performance such as sensitivity, developability, and developing adhesion. In addition, since the carbodole resin has high solvent resolubility, it is preferable from the viewpoint that a coloring resin composition without agglomerates can be designed even with a high color concentration.

As the carbodole resin, preferably, for example, a polymerizable compound represented by the following general formula (B) described in JP 2007-119720 A, and an epoxy having a 茀 skeleton described in JP 2006-308698 The reactant (polycondensate) of base (meth)acrylate resin and polybasic acid, etc.

[化6]

(Here, in the above general formula (B), X represents a group represented by the following general formula (D), Y each independently represents a polycarboxylic acid or its anhydride, and R ⁱ represents a group represented by the following general formula (C) Base, j is an integer from 0 to 4, k is an integer from 0 to 3, and n is an integer from 1 or more.)

[化7]

(Here, 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]

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

The cardole resin used in the present invention can be made into an epoxy compound of a bisphenol compound by, for example, epoxidizing a bisphenol compound, and reacting it with (meth)acrylic acid to form an epoxy group (methyl) Acrylate resin is obtained by reacting a polybasic acid or its anhydride with this epoxy (meth)acrylate resin.

As the bisphenol compound, in the above general formula (D), R ^v is -O-, and this -O- becomes -OH.

As the bisphenol compound, for example, 9,9-bis(4-hydroxyphenyl) pyrene, 9,9-bis(4-hydroxy-3-methylphenyl) pyrene, 9,9-bis(4- Hydroxy-3-methoxyphenyl) pyrene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) pyrene, 9,9-bis(4-hydroxy-3-fluorophenyl)茀, 9,9-bis(4-hydroxy-3-chlorophenyl) 茀, 9,9-bis(4-hydroxy-3-bromophenyl) 茀, 9,9-bis(4-hydroxy-3, Bisphenol compounds such as 5-dichlorophenyl) pyrene, 9,9-bis(4-hydroxy-3,5-dibromophenyl) pyrene, and mixtures thereof.

Examples of the polybasic acid and its anhydride used in the reaction of the epoxy (meth)acrylate resin having a phosgene skeleton include maleic acid, succinic acid, itaconic acid, phthalic acid, and tetrahydrophthalic acid. , Hexahydrophthalic acid, methyl tetrahydrophthalic acid, methyl endomethylene tetrahydrophthalic anhydride, chloro-bridged anhydride, glutaric acid and other dicarboxylic acids or their anhydrides; biphenyltetracarboxylic acid, two Phenyl ketone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, biphenyl tetracarboxylic acid, 4-(1,2-dicarboxyethyl)-1,2,3,4-tetrahydronaphthalene-1, 2-Dicarboxylic acid, butane tetracarboxylic acid, coke honey Tetracarboxylic acids such as tartaric acid or these acid dianhydrides; trimellitic acid or tricarboxylic acids such as trimellitic acid or its anhydrides or its acid anhydrides. These can be used alone or in combination of two or more kinds.

As the carbodole resin used in the present invention, preferably, for example, a ring having a stilbene skeleton is an addition product of a chloroepoxy (meth)acrylic acid derivative and a dicarboxylic anhydride and/or tetracarboxylic dianhydride. Oxy (meth)acrylate acid adduct.

As a commercially available product name of a cardinal resin that can be used in the present invention, for example, INR-16M (manufactured by Nagase ChemteX Co., Ltd.) and the like can be mentioned.

The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, respectively, and may use 2 or more types together.

The alkali-soluble resin used in the photosensitive colored resin composition for color filters can be used singly or in combination of two or more. There is no particular limitation on its content, and it is relative to the photosensitive color filter for color filters. The total solid content of the colored resin composition, the alkali-soluble resin is preferably in the range of 5-60% by mass, more preferably 10-40% by mass. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin exceeds the above upper limit, film roughness or patterns may occur during development. Falling off the situation. Furthermore, in the present invention, the solid content is an owner other than the above-mentioned solvent, and also includes liquid polyfunctional monomers and the like.

<Multifunctional monomer>

The polyfunctional monomer used in the photosensitive colored resin composition for color filters may be polymerizable by using a photoinitiator described later, and the rest is not particularly limited. Usually, two or more monomers can be used. The compound with an ethylenically unsaturated double bond is particularly preferably a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups.

As such a polyfunctional group (meth)acrylate, it can select suitably from a conventionally well-known thing, and can use it. Specific examples include those described in JP 2013-029832 A, etc.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the photosensitive colored resin composition for color filters 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, poly(meth)acrylates of trivalent or higher polyols, or these dicarboxylic acid modifiers, specifically, more preferably: trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, succinic acid modification product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Ester, dipentaerythritol penta(meth)acrylate modified by succinic acid, dipentaerythritol hexa(meth)acrylate, etc.

The content of the polyfunctional monomer used in the photosensitive colored resin composition for color filters is not particularly limited. Compared to the total solid content of the photosensitive colored resin composition for color filters, the polyfunctional group The monomer is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass. If the content of the polyfunctional monomer is less than the above lower limit, the photocuring cannot be carried out sufficiently, and the exposed part may be eluted during development, and if the content of the polyfunctional monomer is more than the above upper limit, The alkali developability may be reduced.

<Photoinitiator>

The photoinitiator used in the photosensitive colored resin composition for a color filter is not particularly limited, and it can be used from various known photoinitiators alone or in combination of two or more. Specific examples include, for example, Japanese Patent Laid-Open No. 2013-029832 Those recorded in the newspaper, etc.

As a photoinitiator, only 1 type may be used, and 2 or more types may be used together. As the photoinitiator, it is preferable to contain an oxime ester-based photoinitiator from the viewpoint of the high effect of suppressing the occurrence of pattern peeling and the effect of suppressing the occurrence of water bleeding. If a dispersant having an acid value is used, water bleeding tends to occur particularly easily, but it is suitable for use from the viewpoint that water bleeding can be suppressed by using an oxime ester-based photoinitiator in combination. In addition, the so-called water bleeding refers to the phenomenon that traces like water bleeding occur after alkaline development and after rinsing with pure water. This kind of water bleeding disappears after post-baking, so there is no problem as a product, but during the appearance inspection of the pattern surface after development, it will be detected as uneven and abnormal, causing the problem that normal products and abnormal products cannot be distinguished. . Therefore, if the inspection sensitivity of the inspection device is reduced during the appearance inspection, it will result in a decrease in the yield of the final color filter manufacturing, which becomes a problem.

As the oxime ester-based photoinitiator, from the viewpoint of reducing contamination of the photosensitive colored resin composition for color filters or device contamination caused by decomposition products, those having an aromatic ring are preferred, and more preferred Those having a condensed ring containing an aromatic ring, and more preferably those having a condensed ring containing a benzene ring and a heterocyclic ring.

As the oxime ester-based photoinitiator, 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzyl)], ethyl ketone, 1-[9-ethyl Group-6-(2-methylbenzyl)-9H-carbazol-3-yl)-,1-(o-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, JP 2001- The oxime ester-based photoinitiators described in Bulletin No. 233842, JP 2010-527339, JP 2010-527338, JP 2013-041153, etc. are appropriately selected. As commercially available products, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (the above are made by BASF), ADEKA OPT-N-1919, ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-831 (the above are ADEKA Corporation), TR-PBG-304, TR-PBG-326, TR-PBG-3057 (the above are manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), etc.

As the oxime ester-based photoinitiator used in the present invention, in order to use PG59 to achieve a wider color reproduction gamut and increase the color material concentration, the photosensitive colored resin composition has excellent curability, development resistance, and pattern peeling. In terms of its inhibitory effect and the superior effect of inhibiting the occurrence of water bleeding, it is preferable to use an oxime ester-based photoinitiator that generates alkyl radicals, and more preferably an oxime ester-based photoinitiator that generates methyl radicals. Beginner. It is presumed that alkyl radicals are easier to move and activate radicals than aryl radicals. Examples of the oxime ester-based photoinitiator that generates alkyl radicals include ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl ]-,1-(O-acetyl oxime) (trade name: Irgacure OXE-02, manufactured by BASF), ketone, [8-[[(acetyloxy)imino][2-(2,2 ,3,3-Tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-,(2,4,6 -Trimethylphenyl) (trade name: Irgacure OXE-03, manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxy Phenyloxy)-9H-carbazol-3-yl)-,1-(o-acetyloxime) (trade name ADEKA OPT-N-1919, manufactured by ADEKA), ketone, (9-ethyl- 6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyloxime) (trade name ADEKA AKLS NCI-831, manufactured by ADEKA), 1-acetone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl ]-,1-(O-acetyl oxime) (trade name TR-PBG-304, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1-acetone, 3-cyclopentyl-1-[2-(2-pyrimidine sulfide) Group)-9H-carbazol-3-yl)-,1-(o-acetyloxime) (trade name TR-PBG-314, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), ethyl ketone, 2-cyclohexyl-1 -[2-(2-pyrimidinyloxy)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (trade name TR-PBG-326, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Ethyl ketone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (trade name TR-PBG-331, Changzhou Qiangli Electronic New Material company), 1-octanone, 1-[4-[3-[1-[(acetoxy)imino]ethyl]-6-[4-[(4,6-dimethyl -2-pyrimidinyl)sulfanyl]-2-methylbenzyl]-9H-carbazol-9-yl]phenyl]-,1-(o-acetyloxime) (trade name EXTA-9, UNION CHEMICAL company system) and so on.

啉基丙烷-1-酮(例如Irgacure 907、BASF公司製)、2-苄基-2-(二甲基胺基)-1-(4-

啉基苯基)-1-丁酮(例如Irgacure 369，BASF公司製)、4,4'-雙(二乙基胺基)二苯基酮(例如Hicure ABP，川口藥品製)等。 In addition, in the oxime ester-based photoinitiator, it is preferable to use a photoinitiator having a tertiary amine structure in combination from the viewpoint of sensitivity improvement. The reason is that the photoinitiator with a tertiary amine structure has a tertiary amine structure in the molecule that is an oxygen quencher, so the free radicals generated by the initiator are not easily deactivated by oxygen, which can improve sensitivity Caused by. As a commercially available product of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-

Alkylpropan-1-one (e.g. Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-

(Alolinylphenyl)-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 color filters is not particularly limited. Compared with the total solid content of the photosensitive colored resin composition for color filters, the photoinitiator is more It is preferably in the range of 3-40% by mass, more preferably 10-30% by mass. If the content is less than the above lower limit, the photohardening cannot be sufficiently performed, and the exposed part may be eluted during development; on the other hand, if the content is more than the above upper limit, the yellowing property of the resulting colored layer may become stronger. When the brightness is reduced.

<Optional ingredients>

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

As additives, in addition to antioxidants, for example, polymerization stoppers, chain Moving agents, leveling agents, plasticizers, surfactants, defoamers, silane coupling agents, ultraviolet absorbers, adhesion promoters, etc.

In the photosensitive colored resin composition for color filters of the present invention, from the viewpoint of heat resistance, it is preferable to further contain an antioxidant. The antioxidant may be appropriately selected from conventional ones. Specific examples of antioxidants include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, etc. From the viewpoint of heat resistance, it is preferable to use hindered antioxidants. Phenolic antioxidants.

In the case of using antioxidants, there are no particular limitations on the amount of antioxidants blended in a range that does not impair the effects of the present invention. The amount of antioxidants blended is relative to the solid content in the photosensitive colored resin composition for color filters In total, the antioxidant is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 4.0% by mass. If it is more than the above-mentioned lower limit, heat resistance is excellent. On the other hand, if it is below the above upper limit, the photosensitive colored resin composition for color filters of the present invention can be made into a high-sensitivity photosensitive colored resin composition for color filters.

Moreover, as a specific example of a surfactant and a plasticizer, what is described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned, for example.

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

The total content of the color material is preferably 3 to 65% by mass, more preferably 4 to 60% by mass relative to the total solid content of the photosensitive colored resin composition for color filters. If it is more than the said lower limit, when the photosensitive colored resin composition for color filters is apply|coated to a predetermined film thickness (usually 1.0-5.0 micrometers), the colored layer can have sufficient color density. Moreover, if it is less than the said upper limit, it is excellent in storage stability, and at the same time, it can obtain the coloring layer which has sufficient hardness, or the adhesiveness with a board|substrate. Especially in forming In the case of a coloring layer with a high color material concentration, the color material content is preferably formulated at a ratio of 15-65% by mass, more preferably 25-60% by mass relative to the photosensitive colored resin composition for color filters.

In addition, the content of the dispersant is not particularly limited on the premise that the color material can be uniformly dispersed. For example, 1-40 mass can be used relative to the total solid content of the photosensitive colored resin composition for color filters. %. Moreover, it is preferable to mix 2-30 mass% with respect to the total solid content of the photosensitive colored resin composition for color filters, and it is especially preferable to mix 3-25 mass %. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of the photosensitive colored resin composition for color filters will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially when forming a coloring layer with a high color material concentration, the dispersant content is preferably 2-25% by mass, more preferably 3-20% by mass relative to the photosensitive colored resin composition for color filters. In addition, the quality of the dispersant in the case of the salt-type block copolymer is the combination of the block copolymer before the salt formation and one or more compounds in the group consisting of the general formulas (1) to (3). Total quality.

In addition, the content of the solvent may be appropriately set within the range in which the colored layer can be formed accurately. It is usually preferably in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass, relative to the total amount of the photosensitive colored resin composition for color filters containing the solvent. When the content of the above-mentioned solvent is within the above-mentioned range, it can be made to be excellent in coatability.

<Manufacturing Method of Photosensitive Colored Resin Composition for Color Filter>

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

I-3. The first color filter related to the present invention

The first color filter related to the present invention is one having at least a transparent substrate and a coloring layer provided on the transparent substrate, and is characterized in that at least one of the coloring layers has a feature that makes the first invention related to the first The color filter is a colored layer formed by curing a photosensitive colored resin composition.

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 the 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>

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

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

In addition, the arrangement of the colored layers is not particularly limited, and it can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type. In addition, the width, area, etc. of the colored layer can be arbitrarily set.

The thickness of the colored layer is appropriately controlled by the coating method, adjusting the solid content concentration or viscosity of the photosensitive colored resin composition for color filters, etc., usually 1~5μm Range.

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

First, the above-mentioned photosensitive colored resin composition for a color filter of the present invention is applied to the following coating method using coating means such as spray coating, dip coating, bar coating, roll coating, spin coating, and die coating. On the transparent substrate, a wet coating film is formed. Among them, the spin coating method and the die coating method are preferably used.

Next, after drying the wet coating film using a hot plate or oven, etc., it is exposed through a mask with a predetermined pattern, and the alkali-soluble resin and the polyfunctional monomer are photopolymerized to form a curing涂膜。 Coating. As a light source used for exposure, ultraviolet rays, electron beams, etc., such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, are mentioned, for example. The amount of exposure is appropriately adjusted according to the light source used or the thickness of the coating film.

Furthermore, in order to promote the polymerization reaction after exposure, heat treatment may be performed. The heating conditions are appropriately selected in accordance with the blending ratio of the components in the photosensitive colored resin composition for color filters used, the thickness of the coating film, and the like.

Secondly, a developing solution is used to perform a development process, and by dissolving and removing the unexposed part, a coating film is formed according to the desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is generally used. In this alkaline solution, an appropriate amount of surfactants, etc. can also be added. In addition, a general method can be adopted as the development method.

After the development process, washing with a developing solution is usually performed, and the cured coating film of the photosensitive colored resin composition for color filters is dried to form a colored layer. In addition, after the development treatment, heat treatment may be performed in order to sufficiently harden the coating film. The heating conditions are not particularly limited, and can be appropriately selected according to the application of the coating film.

<Shading part>

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

The pattern shape of the light-shielding portion is not particularly limited, and examples include shapes such as a stripe shape and a matrix shape. The light-shielding part may be a metal thin film such as chromium formed by a sputtering method, a vacuum vapor 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 a resin adhesive. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, and a thermal transfer of the photosensitive resist. Printing methods, etc.

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

<Transparent substrate>

As the transparent substrate in the color filter of the present invention, it is not particularly limited as long as it is a transparent substrate for visible light, and a transparent substrate used in general color filters can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates; or transparent and flexible materials such as transparent resin films, optical resin plates, and flexible glass.

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

In addition, the color filter of the present invention can form, for example, a protective layer or a transparent electrode layer, or even an alignment film or alignment protrusions, column spacers, etc. in addition to the above-mentioned transparent substrate, light-shielding portion and coloring layer.

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

The first liquid crystal display device of the present invention is characterized by having the color filter according to the first 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 diagram showing an example of the 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, a counter substrate 20 having a TFT array substrate, etc., and is formed between the color filter 10 and the counter substrate 20. The liquid crystal layer 30.

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

The driving method of the liquid crystal display device of the present invention is not particularly limited, and the driving method used in general liquid crystal display devices can be adopted. Such driving methods include, for example, the TN method, IPS method, OCB method, and MVA method. In the present invention, any of these modes can be suitably used.

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

Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy, and mixtures thereof can be used in accordance 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 of producing a liquid crystal cell can be used, for example, a vacuum injection method or a liquid crystal dropping method.

In the vacuum injection method, for example, a color filter and a counter substrate are used in advance to make a liquid crystal cell. The liquid crystal is heated to make an isotropic liquid, and then the capillary effect is used to inject the liquid crystal into the liquid crystal in the state of the isotropic liquid. In the cell, the liquid crystal layer can be formed by sealing with an adhesive. Thereafter, the liquid crystal cell is slowly cooled to room temperature, and the enclosed liquid crystal can be aligned.

Furthermore, in the liquid crystal dropping method, for example, a sealant is applied to the edge of a color filter, and then the color filter is heated to a temperature at which the liquid crystal becomes an isotropic phase, and the liquid crystal is isotropic with a dispenser or the like. It is dripped in a liquid state, the color filter and the counter substrate are overlapped under reduced pressure, and the liquid crystal layer can be formed by adhering it through a sealant. Thereafter, the liquid crystal cell is slowly cooled to room temperature, and the enclosed liquid crystal can be aligned.

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

The first organic light-emitting display device related to the present invention is characterized by having the above-mentioned 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 diagram showing an example of the organic light emitting display device of the present invention. As shown 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 can also be provided between the color filter 10 and the organic light-emitting body 80.

As a method of stacking the organic light-emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the color filter. Method; or a method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60, etc. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, and the luminescence in the organic light emitting body 80 For the layer 74, the electron injection layer 75, the cathode 76, and other configurations, known materials can be appropriately used. The organic light emitting display device 100 manufactured in this way is, for example, applicable to an organic EL display in a passive driving mode, and also applicable to an organic EL display in an active driving mode.

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

II. The second invention

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

II-1. The second color material dispersion liquid related to the present invention

(i) The second embodiment of the first embodiment of the present invention

The second color material dispersion liquid for the color filter of the first 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 above-mentioned color material contains C.I. Pigment Green 59;

The above-mentioned dispersant is a polymer having a structural unit represented by the following general formula (I).

[化9]

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

In the second color material dispersion liquid related to the first embodiment of the present invention, the color material contains CI Pigment Green 59 (hereinafter sometimes abbreviated as PG59), and a polymer having a structural unit represented by general formula (I) is used in combination. Therefore, a green color material dispersion with bluish green color, excellent color material dispersion stability, and high brightness can be obtained.

In the second invention, since PG59 is used as the color material, a chromaticity region that cannot be achieved by PG58 can be achieved. Furthermore, since a polymer having a structural unit represented by the general formula (I) is used in combination, it can be made to achieve high brightness Color filters with large triangles connected by 3 dots of red, green, and blue pixels, and excellent color reproducibility.

In addition, the second color material dispersion liquid of the first embodiment of the present invention, since PG59 is combined with a polymer having a structural unit represented by the general formula (I) as a dispersant, it can be produced with excellent color material dispersion stability and solvent A photosensitive colored resin composition with excellent resolubility. Since the color material containing PG59 is combined with a polymer having the structural unit represented by the general formula (I) as a dispersant, it is presumed that the color material containing PG59 strongly adsorbs the nitrogen contained in the structural unit represented by the general formula (I) The color material has superior dispersibility due to the location, and the color material containing PG59 that is firmly adsorbed on the nitrogen site and surrounded by the dispersant can be easily washed away by the re-dissolvable solvent while still adsorbing on the dispersant. In addition, when a color material containing PG59 is combined with a polymer having a structural unit represented by the general formula (I) as a dispersant, there is a tendency to easily suppress the occurrence of development residue. The reason is presumed to be that the color material containing PG59 that is firmly adsorbed on the nitrogen site and surrounded by the dispersant is easily washed away in the state of being adsorbed on the dispersant during development, and the color material does not remain on the substrate, and it is easy to suppress the occurrence of development residues. .

(ii) The second embodiment of the present invention

The second color material dispersion liquid for color filters of the second 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 above color material contains C.I. Pigment Green 59 and yellow color material;

Examples of the above-mentioned dispersant include a polymer having a structural unit represented by the above-mentioned general formula (I).

In the color material dispersion liquid related to the second embodiment of the present invention, the color material contains PG59 and yellow color material, and a polymer having a structural unit represented by general formula (I) is used in combination as a dispersant, so it can be It forms a colored layer with excellent dispersion stability of the color material, suppression of display defects, and high brightness and excellent color reproducibility.

In the second invention, PG59 is used as a color material which is a single color and exhibits bluish green with strong coloring power and high brightness. Therefore, by combining with yellow color material, even if the content of PG59 in the color material is suppressed, Or suppress the P/V ratio ((the mass of the color material in the composition)/(the mass of the solid content other than the color material in the composition) ratio), and the green contained in the above-mentioned high color density green area can still be produced Pixel. The reason why poor display easily occurs in green pixels is presumably due to the green color material with phthalocyanine skeleton. However, if the color material dispersion of the present invention is used, the green color material with phthalocyanine skeleton can be reduced in pixels. In addition, the above-mentioned P/V ratio can be reduced, so it is estimated that a green pixel with suppressed display failure can be achieved.

In addition, in the second aspect of the present invention, PG59 is used as a color material, and it is possible to achieve a chromaticity region that PG58 cannot achieve in the above-mentioned high color density green region. Furthermore, in the second embodiment of the present invention, since PG59 and the yellow color material are used in combination with the polymer having the structural unit represented by the general formula (I), the color material dispersibility and color material dispersion are The stability is superior, and it can be made into a color filter that achieves high brightness or high contrast, and is connected by three points of red, green, and blue pixels with a larger triangle and excellent color reproducibility.

In addition, the second color material dispersion liquid of the second embodiment of the present invention has a polymer having a structural unit represented by the general formula (I) in combination with PG59 and yellow color material as a dispersant, so it can be made solvent-resoluble Excellent photosensitive colored resin composition. It is presumed that since PG59 and the yellow color material are combined with the polymer having the structural unit shown in the general formula (I) as the dispersant, the PG59 and the yellow color material that are firmly adsorbed to the nitrogen site and surrounded by the dispersant are easy to remain adsorbed to the dispersion The state of the agent is washed away by the resolubilizing solvent.

In the color material dispersion liquid for color filters according to the second embodiment of the present invention, the above-mentioned PG59 is preferably from the viewpoint of suppressing the occurrence of display failures and enhancing color reproducibility and increasing brightness. Contains 5-95% by mass in the above-mentioned color materials.

The second aspect of the color material dispersion liquid for color filters of the second embodiment of the present invention is that from the viewpoint of easy formation of a colored layer that suppresses the occurrence of display defects, high brightness and high contrast, and excellent color reproducibility, the yellow The color material is preferably selected from CI Pigment Yellow 138 (hereinafter sometimes referred to as PY138), CI Pigment Yellow 139 (hereinafter sometimes referred to as PY139), CI Pigment Yellow 185 (hereinafter sometimes referred to as PY185), CI Pigment Yellow 150 (Hereinafter sometimes referred to as PY150) and one or more of its derivative pigments.

In the color material dispersion liquid for a color filter according to the second embodiment of the second aspect of the present invention, the above-mentioned color material system, in addition to PG59, preferably contains at least one of C.I. Pigment Green 58 and C.I. Pigment Green 7. Among them, from the viewpoint of achieving the target chromaticity, suppressing display defects, and forming high-brightness green pixels, it is preferable to include PG58 in addition to PG59. On the other hand, from the viewpoint of achieving the target chromaticity, suppressing display failure, further reducing the above-mentioned P/V ratio, and improving plate-making properties such as development resistance, it is preferable to contain PG7 in addition to PG59. Also, by achieving the target chromaticity and suppressing display failure From the viewpoint of improving the balance of brightness and improving plate-making performance due to the reduction of the above-mentioned P/V ratio, it is preferable to include PG58 and PG7 in addition to PG59.

(iii) The second third embodiment of the present invention

The second color material dispersion liquid for color filters according to the third embodiment of the present invention is a color material dispersion liquid for color filters containing a color material, a dispersant, and a solvent, and is characterized by:

The above color material contains CI pigment green 59, blue color material and yellow color material; the yellow color material series (Y1) contains at least one yellow color material of CI pigment yellow 185, or (Y2) uses CI pigment yellow 139 as an essential component , Further containing at least two yellow color materials selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150 and its derivative pigments;

Examples of the above-mentioned dispersant include a polymer having a structural unit represented by the above-mentioned general formula (I).

The second color material dispersion liquid related to the third embodiment of the present invention contains the above-mentioned specific color material, and the polymer having the structural unit represented by the above general formula (I) is used in combination as a dispersant, so that the color material can be formed The coloring layer has excellent dispersion stability, suppresses the occurrence of display defects, and has high brightness and excellent color reproducibility.

According to the second color material dispersion liquid related to the third embodiment of the present invention, it is estimated that by combining either the above (Y1) or the above (Y2) as the yellow color material with PG59 and the blue color material, the efficiency Good absorption of wavelengths that are not fully absorbed by PG59 and blue color materials, reducing the total amount of color materials, which can also reduce the above-mentioned P/V ratio and reproduce colors. Therefore, among the above-mentioned high-density greenness, the high-density green (x=0.14~0.30, y=0.61~0.75) region, and further (x=0.14~0.30, y=0.66~0.75) can be achieved, suppressing Poor display, forming a high-brightness colored layer.

In addition, when the above-mentioned specific yellow color material is combined with a specific dispersant 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 second color material dispersion liquid of the third embodiment of the present invention, from the viewpoint of brightness, the blue color material preferably contains at least one of C.I. Pigment Blue 15:3 and C.I. Pigment Blue 15:4.

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 within a range that does not impair the effects of the present invention.

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

<color material>

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

PG59 is used as the chromaticity coordinates in the XYZ color system of JIS Z8701 measured by a single light source with C light source. It can be expressed as a color material of x=0.10~0.30, y=0.30~0.64, where x= 0.13~0.20, y=0.32~0.60 is the characteristic color material.

PG59 is in the XYZ color system of JIS Z8701 measured by a single light source with C light source. It can be represented by the xy chromaticity coordinate region enclosed by the following equations 1, 2 and 3.

(Equation 1) y=6.715×x-0.286

Among them, 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

Among them, 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

Among them, in Equation 3, 0.121<x<0.310

Among the xy chromaticity coordinate regions enclosed by the above equations 1, 2 and 3, the region of x=0.13~0.20 and y=0.32~0.60 is the most characteristic and effective.

When the PG59 used in the present invention sets the transmittance at 450nm to 5%, the wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum of 400~700nm becomes the maximum is 505~535nm. Furthermore, the transmittance of the above-mentioned wavelength (Tmax) is 70% or more. In addition, the PG59 used in the present invention has a transmittance of 15% or less of the above-mentioned spectral transmittance spectrum at 435 nm, and the transmittance of the above-mentioned spectral transmittance spectrum at 575 nm is below 5%.

In order to coat PG59 as a monomer and measure color, a suitable dispersant, binder component and solvent are prepared in PG59 to prepare a coating liquid, which is coated on a transparent substrate, dried, and cured as needed. As a binder component, a non-curable thermoplastic resin composition can also be used on the premise that a transparent coating that can be used for color measurement can be formed, and a photocurable (photosensitive) or thermosetting resin composition can also be used. Things. In addition, in the photosensitive colored resin composition of the present invention 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 also be performed.

As a clear coating that contains dispersant and adhesive components and can be used for color measurement, for example, the thickness of the film can be 2.0μm, and the transmittance of the spectral transmittance spectrum of 380~780nm is 95% or more. As the standard.

Furthermore, the spectroscopic transmittance spectrum can be measured using a spectroscopic measuring device (for example, a microscope OSP-SP200 manufactured by Olympus). The measurement condition is C light source.

In addition, in the color material dispersion of the present invention, PG59 alone may also be used as a color material. On the other hand, without prejudice to the effect of the present invention, PG59 can also be combined with color materials that are different from PG59 as exemplified in the first color material item of the color material dispersion liquid of the present invention as other colors. material. As other color materials, for example, other green color materials, yellow color materials, or blue color materials are suitably used.

In the second color material dispersion liquid related to the present invention, when other color materials different from PG59 are used, the content of PG59 can be adjusted appropriately according to the required chromaticity, and there is no particular limitation. Among them, from the viewpoint of increasing color reproducibility and increasing brightness, it is preferable to contain PG59 in an amount of 5% by mass or more, and more preferably 10% by mass or more with respect to the entire color material containing PG59.

In addition, in the second color material dispersion liquid related to the present invention, it is preferable to further use PG59 in combination from the viewpoint of suppressing the occurrence of display defects of green pixels and forming a color layer with high brightness and excellent color reproducibility The yellow color material is used as the color material. (Second Embodiment of the Invention)

Examples of yellow color materials include 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 CI Pigment Yellow 150 derivative pigments.

As the derivative pigment of C.I. Pigment Yellow 150, specific examples include Metal complexes of mono-, di-, tri-, and tetra-anions of an azo compound of the following chemical formula (i) or following one of its tautomeric structures and a metal in which at least one guest compound acts as the host, as the above-mentioned metal, Examples include Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn, and La. As the metal, Ni is suitable, and more preferably at least one of the above-mentioned C.I. Pigment Yellow 150 derivative pigment containing Ni and Zn, and the above-mentioned C.I. Pigment Yellow 150 derivative pigment containing Ni and Cu. Among them, it is preferable to be based on the ratio of Ni:Zn=8:2~2:8 (molar ratio) of the above-mentioned CI pigment yellow 150 derivative pigment containing Ni and Zn, and based on Ni:Cu=5:5~9.8 : At least one of the above-mentioned CI Pigment Yellow 150 derivative pigments containing Ni and Zn in a ratio of 0.2 (molar ratio).

[化10]

(In the above chemical formula (i), R is independently OH, NH ₂ , NH-CN, acylamino or arylamino, and R'is independently -OH or -NH ₂ )

For CI Pigment Yellow 150 and its derivative pigments, please refer to Japanese Patent Application Publication No. 2001-354869, Japanese Patent Application Publication No. 2005-325350, Japanese Patent Application Publication No. 2007-25687, Japanese Patent Application Publication No. 2007-23287, Japanese Patent Application Publication No. 2007- Obtained from Bulletin No. 23288 and Special Publication No. 2008-24927.

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

In the second color material dispersion of the present invention, the yellow color material is appropriately selected, and can be used singly or as a mixture of two or more. As a better yellow color material, It is preferable to use the same yellow color material for the same reasons as those described in the photosensitive colored resin composition for color filters described later.

In addition, in the color material dispersion liquid of the second embodiment of the present invention, it is also possible to use PG59 in combination with a yellow color material in the color material dispersion liquid of the second embodiment of the present invention, as illustrated below Other color materials. As other color materials, for example, other green color materials, blue color materials, and orange color materials are suitably used. Examples of other green color materials different from PG59 include phthalocyanine green pigments such as PG58, PG7, and PG36. As a preferable other color material, it is preferable to use the same other color material for the same reason as described in the photosensitive colored resin composition for color filters mentioned later.

In the second color material dispersion of the present invention, when other green color materials are further contained, from the viewpoint of suppressing the occurrence of display failures and easily achieving a high-brightness colored layer, it is preferable to use a yellow color material in combination with PY150 At least one of its derivative pigments, and PY138.

In the color material dispersion liquid related to the second embodiment of the present invention, the content ratio of PG59 to the entire color material, the content ratio of yellow color material to PG59, and when PG59 and yellow color material and other color materials are used The content ratio of is preferably the same as the content ratio of the photosensitive colored resin composition described later. Among them, the color material dispersion liquid can appropriately mix and use two or more kinds to produce a photosensitive colored resin composition, and it can be suitably used even if it is not set to the same content ratio as the photosensitive colored resin composition described later.

In addition, in the second color material dispersion liquid related to the present invention, as the color material, PG59 is a combination of blue color material and yellow color material, and the yellow color material is preferably (Y1) containing at least one yellow color material of PY185; Or (Y2) PY139 is used as an essential ingredient, and further contains one of the group of pigments selected from the group consisting of PY138, PY150 and PY150 derivatives At least two types of yellow color materials (the second third embodiment of the present invention).

The blue color material in the present invention is a case where the spectral transmittance spectrum is measured in the same manner as 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.

As a blue color material, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. are mentioned, for example. Among the dispersible dyes described in the photosensitive colored resin composition described later, a color material in the range of the above-mentioned blue color material can be appropriately selected and used.

In the second color material dispersion liquid of the third embodiment of the present invention, the blue color material is appropriately selected, and can be used alone or in combination of two or more.

Among them, as the second blue color material used in the third embodiment of the present invention, when PG59 is combined with the above-mentioned specific yellow color material, from the viewpoint of suppressing the decrease in brightness, or by combining the above-mentioned specific dispersion From the viewpoint of superior dispersibility during formulation, β-type copper phthalocyanine pigments are preferred, and among them, at least one of CI Pigment Blue 15:3 and CI Pigment Blue 15:4 is preferred. These β-type copper phthalocyanines The cyanine pigment preferably contains 60% by mass to 100% by mass in the total amount of the blue color material.

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

In the third embodiment of the second aspect of the present invention, (Y1) contains at least one yellow color material of PY185. In addition to PY185, it may further contain other yellow color materials. Examples of the yellow color material include PY1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, Derivatives of 166, 168, 175 and PY150 料 etc.

In the third embodiment of the second aspect of the present invention, as a yellow color material in combination with PY185, it has excellent dispersion stability of the color material, suppresses the occurrence of display defects, and easily achieves a colored layer with high brightness and excellent color reproducibility. In other words, it is preferably at least one selected from the group consisting of PY139, PY150 and their derivative pigments.

In addition, in the third embodiment of the second aspect of the present invention, PY139 is an essential component as (Y2), and at least two yellow color materials selected from the group consisting of PY138, PY150 and their derivative pigments In addition to the above-mentioned at least two yellow color materials, the system may further contain other yellow color materials. Examples of the yellow color materials include PY1, 3, 12, 13, 14, 15, 16, 17, 20, 24 , 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117 , 119, 120, 126, 127, 128, 129, 151, 152, 153, 154, 155, 156, 166, 168 and 175 etc.

In the third embodiment of the second aspect of the present invention, when the above-mentioned (Y1) is used as the yellow color material, since it is easy to achieve higher brightness, it is preferable. On the other hand, in the case of using the above-mentioned (Y2) as the yellow color material, since high contrast is easily achieved, it is preferable.

In the third embodiment of the second aspect of the present invention, PY139 is used as an essential component as the above-mentioned (Y2), and at least two yellow color materials selected from the group consisting of PY138, PY150 and their derivative pigments are further included. Among them, from the viewpoint of suppressing the occurrence of display defects and easily achieving a high-brightness and high-contrast colored 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 kinds of yellow color materials.

In addition, in the color material dispersion liquid of the third embodiment of the second aspect of the present invention, without impairing the effects of the present invention, PG59, blue color material, and the above-mentioned specific yellow color material can also be used in combination with photosensitive materials described later Other color materials exemplified in the colored resin composition. As other color materials, for example, other green color materials, or orange color materials are suitably used. As suitable other color materials, it is preferable to use the same other color materials for the same reasons as those described in the photosensitive colored resin composition for color filters described later. In addition, the green color material in the present invention refers to a color material having a peak top in the range exceeding 490 nm and 580 nm or less when the spectral transmittance spectrum is measured as described above.

In the color material dispersion liquid of the third embodiment of the present invention, the content ratios of PG59, blue color material, and yellow color material, and the content ratio when other color materials are used, are preferably set to be the same as the photosensitive material described below. The content ratio of the colored resin composition is the same. Among them, the color material dispersion liquid can appropriately mix and use two or more kinds to produce a photosensitive colored resin composition, so it is suitable for use even if it is not set to the same content ratio as the photosensitive colored resin composition described later.

As the second average primary particle size of the color material used in the present invention, or the average dispersed particle diameter of the color material in the color material dispersion liquid, it can be compared with the color material item in the first color material dispersion liquid of the present invention. The description is the same, so the description is omitted here.

In addition, since the content of the color material in the color material dispersion liquid of the second invention can be the same as that described in the color material item of the color material dispersion liquid related to the first invention, the description is omitted here.

<Dispersant>

In the second aspect of the present invention, a polymer having a structural unit represented by the above general formula (I) is used as a dispersant. The constituent units represented by the above general formula (I) are alkaline and play a role in It should be the function of the color material as the adsorption part.

The second color material dispersion liquid related to the present invention improves the absorption performance of the color material and improves the dispersion and dispersion stability of the color material by using a polymer having the structural unit shown in the general formula (I).

Since the constituent unit represented by the above general formula (I) can be the same as that described in the first item of the dispersant in the color material dispersion liquid related to the present invention, the description is omitted here.

In the polymer having the structural unit represented by the above general formula (I), the above general At least a part of the terminal nitrogen site of the structural unit represented by formula (I) is a salt formed with one or more compounds selected from the group consisting of 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 first item of the salt-type block copolymer of the dispersant in the color material dispersion of the present invention , So the description is omitted here.

[化11]

(The symbols in general formulas (1)~(3) are as above.)

In addition, in the second dispersant used in the present invention, among the polymers having the structural unit represented by the general formula (I), one or more compounds selected from the group consisting of the above general formulas (1) to (3) The content is in the color material dispersion liquid related to the first invention mentioned above The description of the salt-type block copolymer item of the dispersant is the same, so the description is omitted here.

As a polymer having a structural unit represented by the general formula (I), from the viewpoint of improving dispersibility, it is more preferable to contain a portion having solvent affinity. As the solvent affinity site, it is preferable to use a monomer having ethylenic unsaturated bonds that can be polymerized with a monomer derived from the structural unit represented by the general formula (I), and the solvent is blended in a manner having solvent affinity And choose appropriately. As a standard, it is preferable to introduce solvent affinity sites relative to the solvent used in combination, so that the solubility of the polymer at 23° C. becomes 20 (g/100g solvent) or more.

As the second polymer with the structural unit represented by the general formula (I) used in the present invention, the dispersibility and dispersion stability of the color material and the heat resistance of the resin composition can be improved, and it can form high brightness and high From the viewpoint of contrasting the coloring layer, among them, block copolymers or graft copolymers are preferred, and block copolymers are particularly preferred. The following is a detailed description of particularly good block copolymers.

[Block copolymer]

If a block containing the structural unit represented by the above general formula (I) is taken as the A block, the A block has basicity as the structural unit represented by the above general formula (I) and functions as an adsorption site corresponding to the color material. function. In addition, when at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) forms a salt with one or more compounds selected from the group consisting of the following general formulas (1) to (3), The salt forming part functions as a stronger adsorption part relative to the color material. On the other hand, the B block that does not contain the structural unit represented by the above general formula (I) functions as a block having solvent affinity. Therefore, the block copolymer used in the present invention functions as a color material dispersant by sharing the function of the A block adsorbed with the color material and the B block having solvent affinity.

As the second dispersant used in the present invention, a block copolymer having a structural unit represented by the above general formula (I), the amine value of the block copolymer is 40 mgKOH/g or more and 130 mgKOH/g or less, CI Since the dispersibility and dispersion stability of Pigment Green 59 become better, it is better.

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

The amine valence of the salt-type block copolymer is smaller than that of the block copolymer before the salt is formed. However, the salt formation site becomes the same or stronger color material adsorption site as the terminal nitrogen site corresponding to the amine group. Therefore, the salt formation tends to improve the color material dispersibility or the color material dispersion stability. In addition, the salt formation site is the same as the amine group, and if it is too large, it will adversely affect the solvent resolubility. Therefore, in the present invention, the amine value of the block copolymer 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 mgKOH/g or more and 130 mgKOH/g or less, more preferably 0 mgKOH/g or more and 120 mgKOH/g or less.

If it is less than the above upper limit, the compatibility with other components is excellent and the solvent resolubility is good.

{A block}

The A block is a block containing 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, so the description is omitted here.

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

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

The A block is within the scope of achieving the purpose of the invention, and may also have a structural unit other than the structural unit shown in the general formula (I). If it is a structural unit that can be copolymerized with the structural unit shown in the general formula (I), May contain. For example, structural units other than the structural unit represented by the general formula (I) that can be contained as the basic block portion, specifically, for example, the structural unit represented by the general formula (II) described later.

In the A block in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is relative to the total mass of the total structural unit of the A block, and is preferably 50-100% by mass, More preferably 80~100% by mass, most preferably 100% by mass. This is because the higher the ratio of the constituent units shown in the general formula (I), the higher the adsorption force for the color material, and the better the dispersibility and dispersion stability of the block copolymer. In addition, the content ratio of the above-mentioned structural unit is calculated from the packing mass when the A block having the structural unit represented by the general formula (I) is synthesized.

In addition, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is based on the viewpoint that the dispersibility and dispersion stability become good, relative to the total structural unit of the block copolymer The total mass of is preferably 5-60% by mass, more preferably 10-50% by mass. In addition, the content ratio of each constituent unit in the block copolymer is calculated from the packing mass when the block copolymer before salt formation is synthesized.

Furthermore, the structural unit represented by the general formula (I) may have affinity with the color material, and may be composed of one type, or may contain two or more types of structural units.

{B block}

The B block is a block that does not contain the structural unit represented by the above general formula (I). As the B block, it is preferable to use a monomer that can be copolymerized with a structural unit represented by the general formula (I) and has an unsaturated double bond, and a solvent is suitably selected as it is solvent-philic. use. As a standard, it is preferable to introduce the B block in such a way that the solubility of the copolymer at 23° C. becomes 20 (g/100g solvent) or more relative to the solvent used in combination.

As the structural unit constituting the B block, for example, a monomer having an unsaturated double bond that can be copolymerized with a monomer derived from the structural unit represented by the general formula (I), and among them, the following general formula (II) ) Shows the constituent units.

The constituent units represented by the following general formula (II) may be the same as those described in the first item of the dispersant in the color material dispersion liquid related to the present invention, so the description is omitted here.

[化12]

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

The number of constituent units constituting the B block is not particularly limited. From the viewpoint of the effective effect of the solvent affinity part and the color material adsorption part and the improvement of the color material dispersibility, it is preferably 10 to 300, more preferably 10 to 100 Pieces, better 10~70 pieces.

In the B block of the block copolymer, the content ratio of the structural unit represented by the above general formula (II) is based on the viewpoint of improving the solubility of the solvent or the dispersibility of the color material, relative to the total structural unit of the B block Total mass, preferably 50-100 mass%, more Preferably 70~100% by mass. In addition, the content ratio of the above-mentioned structural unit is calculated from the packing mass when synthesizing the B block.

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

The structural unit of the B block may be appropriately selected in accordance with the function as a solvophilic site. The structural unit represented by the above general formula (II) may be composed of one type, or may contain two or more types of structural units. Two or more structural units contained in the B block may be randomly arranged in the block.

In addition, as the above-mentioned dispersant, by using the following dispersant, the color material has excellent dispersion stability, excellent effect of suppressing the generation of development residues, and excellent solvent resolubility, and furthermore, it has high performance when making coloring resin compositions. It is preferable from the viewpoint of developing adhesion; the dispersant is at least one of the following block copolymer (P1) and the following salt type block copolymer (P2);

P1: A block copolymer having an A block containing a structural unit represented by the above general formula (I) and a B block containing a structural unit derived from a carboxyl group-containing monomer;

P2: At least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) of the block copolymer, and 1 selected from the group consisting of the compounds represented by the general formulas (1) to (3) A salt-type block copolymer in which more than one compound forms a salt;

The acid value of the dispersant is 1 mgKOH/g or more and 18 mgKOH/g or less, and the glass transition temperature of the dispersant is 30°C or more.

If the color material concentration is increased and the dispersant content is increased, the amount of binder will be relatively reduced. Since it is small, the colored resin layer is easily peeled off from the base substrate during development. The dispersant has the above-mentioned specific acid value and glass transition temperature by containing the B block containing the structural unit derived from the carboxyl group-containing monomer, so that the developing adhesion is improved. If the acid value is too high, it is presumed that although the developability is excellent, the polarity is too high and peeling easily occurs during development.

Such a dispersant may be the same as described in the above-mentioned first dispersant item used in the color material dispersion liquid of the present invention, so the description is omitted here.

In the second color material dispersion liquid related to the present invention, as a dispersant, at least one type of polymer having a structural unit represented by the above general formula (I) is used, and its content depends on the type of color material used, and further The solid content concentration etc. in the photosensitive colored resin composition for color filters mentioned later are selected suitably.

In the second color material dispersion liquid related to the present invention, the content of the dispersant may be the same as that described for the dispersant used in the first color material dispersion liquid related to the present invention, so the description is omitted here.

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

The second color material dispersion liquid related to the present invention is used as a preliminary preparation for preparing the second photosensitive colored resin composition for color filters related to the present invention described later. In other words, the so-called color material dispersion is prepared in the previous stage of preparing the photosensitive colored resin composition for color filters described later, (the mass of the color material in the composition)/(the color material in the composition) A color material dispersion liquid with a relatively high solid content other than the components). Specifically, the ratio of (mass of color material components in the composition)/(mass of solid content other than the color material components in the composition) is usually 1.0 or more. The second aspect of the present invention The color material dispersion liquid can prepare the second photosensitive colored resin composition for color filters according to the present invention, which is excellent in dispersibility, by mixing the components described below.

II-2. The second photosensitive colored resin composition for color filters of the present invention

(i) The second embodiment of the first embodiment of the present invention

The second 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, Its characteristics are,

The above-mentioned color material contains C.I. Pigment Green 59;

The above-mentioned dispersant is a polymer having a structural unit represented by the above-mentioned general formula (I).

The second embodiment of the photosensitive colored resin composition for a color filter of the present invention can be made into the high-density green region by making the color material contain CI Pigment Green 59. A high-brightness or high-contrast colored layer can be achieved. The second photosensitive colored resin composition for the color filter of the first embodiment of the present invention is made of the same as that described in the second embodiment of the first embodiment of the present invention. It can form a colored layer with excellent solvent resolubility, high brightness and high contrast, and excellent color reproducibility.

(ii) The second embodiment of the present invention

The second photosensitive colored 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, Its characteristics are,

The above color material contains C.I. Pigment Green 59 and yellow color material;

The above-mentioned dispersant can be, for example, a polymerization having a structural unit represented by the following general formula (I) body.

The second aspect of the photosensitive colored resin composition for color filters of the second embodiment of the present invention is that the above-mentioned color material contains CI pigment green 59 and yellow color material, and uses a combination of constituent units represented by general formula (I) When the polymer is used as a dispersant, it has the same effect as that described in the second embodiment of the color material dispersion liquid of the second embodiment of the present invention, so that the color material dispersion stability is excellent and the display failure occurs. A coloring layer that suppresses high brightness and has excellent color reproducibility.

(iii) The second third embodiment of the present invention

As the second aspect, the photosensitive colored resin composition for color filters according to the third embodiment of the present invention contains a color material, a dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent The photosensitive colored resin composition for color filters is characterized by:

The above color material contains CI pigment green 59, blue color material and yellow color material; the yellow color material series (Y1) contains at least one yellow color material of CI pigment yellow 185, or (Y2) uses CI pigment yellow 139 as an essential component , And further containing at least two yellow color materials selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150 and its derivative pigments;

Examples of the above-mentioned dispersant include 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 CI Pigment Green 59, the blue color material, and the specific yellow color material, and when used in combination, it has the above general characteristics. The polymer of the structural unit represented by the formula (I) is used as a dispersant, so it is combined with the third embodiment of the present invention in the second It has the same effect as described in the color material dispersion liquid of the state, so it can form a coloring layer with excellent color material dispersion stability, suppressed display failure, and high brightness and excellent color reproducibility.

The second photosensitive colored resin composition for color filters related to the present invention contains at least a color material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. And within the range of the effect of this invention, you may further contain other components. The following describes the components contained in the second photosensitive colored resin composition for color filters of the present invention. However, the CI Pigment Green 59 and the dispersant, which are essential components among the color materials, are the same as those in the second The description of the color material dispersion liquid of the present invention is the same, so the description is omitted here. In addition, the solvent may be the same as that described in the first color material dispersion of the present invention, so the description is omitted here. In addition, the alkali-soluble resin, the polyfunctional monomer, the photoinitiator, and other components can be the same as those described in the first photosensitive color resin composition for color filters of the present invention, so hereby The description is omitted.

<color material>

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

It is not particularly limited as long as it can produce the desired color when forming the coloring layer of the color filter, and various organic pigments, inorganic pigments, and dispersible dyes can be used alone or in combination of two or more. Among them, organic pigments have high color development and high heat resistance, and are suitable for use. As an organic pigment, for example, a compound classified as a pigment in the color index (C.I.; issued by The Society of Dyers and Colourists), and specific examples include those with a color index (C.I.) number as follows.

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

In addition, the second photosensitive colored resin composition for a color filter according to the present invention is more effective in terms of suppressing the occurrence of display defects of green pixels and forming a colored layer with high brightness and excellent color reproducibility. It is better to use yellow color material in combination with PG59 as the color material. (The second embodiment of the present invention is the second). As the second yellow color material used in the second embodiment of the present invention, it may be the same as that described for the color material dispersion liquid of the second embodiment of the second present invention described above. As the second 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.

Among them, it is preferable that the photosensitive colored resin composition for color filters according to the second embodiment of the present invention contains at least one of PG58 and PG7 in addition to PG59. Among them, from the viewpoint of achieving the target chromaticity, suppressing display failures, and forming high-brightness green pixels, it is preferable to include PG58 in addition to PG59. If PG59 and PG58 are used in combination, compared to using PG58 alone, the color reproducibility can be increased, the P/V ratio can be reduced, and the brightness can also be improved. On the other hand, among them, from the viewpoint of achieving the target chromaticity, suppressing display failure, further reducing the above-mentioned P/V ratio, and improving the plate-making properties such as development resistance, it is preferable to contain PG7 in addition to PG59. In addition, from the viewpoint of achieving the target chromaticity, suppressing display failure, improving brightness, and reducing the above-mentioned P/V ratio and improving plate-making performance, it is preferable to include PG58 and PG7 in addition to PG59.

In the photosensitive colored resin composition for color filters according to the second embodiment of the present invention, the content ratio of PG59 to the entire color material can be adjusted according to the The chromaticity needs to be adjusted appropriately, and it is not particularly limited. Among them, from the viewpoint of suppressing the occurrence of display defects, increasing color reproducibility, and improving brightness, it is preferable to contain 5-95% by mass of PG59, more preferably 10 to 90% by mass relative to the entire color material containing PG59. , Better still 20~80% by mass.

In the photosensitive colored resin composition for color filters according to the second embodiment of the present invention, the content ratio of the yellow color material to PG59 can be adjusted appropriately according to the desired chromaticity, and is not particularly limited. . Among them, from the viewpoint of suppressing the occurrence of display defects and enhancing color reproducibility and increasing brightness, it is preferable to contain 10 to 900 parts by mass of yellow color material, and more preferably 20 to 400, relative to 100 parts by mass of PG59. Mass parts.

In the photosensitive colored resin composition for color filters according to the second embodiment of the present invention, the yellow color material can be appropriately selected, and can be used singly or in combination of two or more. Among them, it is easy to achieve suppressed display. From the viewpoint of a coloring layer with poor occurrence, high brightness and high contrast, and excellent color reproducibility, it is preferably one or more selected from the group consisting of PY138, PY139, PY185, PY150 and their derivative pigments.

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

In addition, PY138 is preferably used to achieve high brightness in the chromaticity region of y=0.550~0.610, x=0.205~0.324, and it is more preferably used to achieve high brightness in the chromaticity region of x=0.246~0.324 The case of high brightness.

In addition, the PY185 series is suitable for widening the color reproduction gamut. In the case of y=0.610~0.626, it is also more suitable for the chromaticity region expressed as x=0.205~0.324, and is better used in It is expressed as the chromaticity region of y=0.659.

In the photosensitive colored resin composition for color filters according to the second embodiment of the present invention, when at least one of PY150 and its derivative pigments are used in combination with PY138, the desired chromaticity is matched , Brightness, and film thickness can be adjusted appropriately, 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 brightness and the above-mentioned P/V ratio, the total amount of at least one of PY150 and its derivative pigments, and the ratio of PY138, is more preferably 10:90~90:10. From the perspective of brightness and P/V From the point of view, it is better to be 20:80~80:20.

In addition, when the photosensitive colored resin composition for a color filter according to the second embodiment of the present invention further contains a green color material other than PG59, the green color material containing PG59 is relative to the entire color material The content ratio can be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoints of suppressing the occurrence of display defects, increasing color reproducibility, and increasing brightness, it is preferable to contain PG59-containing green color material 10 to 90% by mass, and more preferably 20 to 80% by mass relative to the entire color material. .

In addition, the content ratio of the yellow color material to the green color material containing PG59 can be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the viewpoints of suppressing the occurrence of display defects, enhancing color reproducibility, and increasing brightness, it is preferable to contain 10 to 900 parts by mass of yellow color material, and more preferably 20 to 100 parts by mass of green color material containing PG59. 400 parts by mass.

In addition, when the photosensitive colored resin composition for color filters according to the second embodiment of the present invention further contains at least one of PG58 and PG7, it is preferable to the entire green color material containing PG59 It contains at least one of PG58 and PG7 at 5-50% by mass. Among them, the display defect and brightness are compared with the above-mentioned P/V ratio From the viewpoint of, it is more preferable to contain 5-40% by mass, and from the viewpoint of brightness and the above-mentioned P/V ratio, it is still more preferable to contain 5-30% by mass.

In addition, in the photosensitive colored resin composition for a color filter of the second embodiment related to the present invention, the color material may further contain a green color material and a yellow color material within a range that does not impair the effect of the present invention. For color materials other than color materials, the total content of green color materials and yellow color materials containing PG59 is preferably 70-100% by mass, more preferably 80-100% by mass relative to the entire color material.

In addition, in the second photosensitive colored resin composition for color filters related to the present invention, PG59 is used as a color material to combine a blue color material and a yellow color material; the yellow color material system (Y1) contains CI Pigment Yellow 185 At least one yellow color material, or (Y2) takes CI Pigment Yellow 139 as an essential ingredient, and further contains at least two of one or more selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150 and their derivative pigments Yellow color material (the second third embodiment of the present invention). The blue color material and the specific yellow color material used as the second embodiment of the third embodiment of the present invention may be the same as those described in the above-mentioned second embodiment of the third embodiment of the present invention. As the second color material used in the third embodiment of the present invention, it is preferable to use other green color materials and orange color materials.

Among them, in the photosensitive colored resin composition for a color filter according to the third embodiment of the present invention, the second aspect includes achieving the target chromaticity, suppressing poor display, further reducing the above-mentioned P/V ratio, and suppressing development residues. From the standpoint of improving development adhesion and plate-making properties, it is more preferable to contain PG7.

In the photosensitive colored resin composition for color filters of the second embodiment of the present invention, the content ratio of PG59 with respect to the entire color material can be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, by suppressing the occurrence of display defects, From the viewpoint of broadening color reproducibility and improving brightness, 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% by mass relative to the entire color material containing PG59. %.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the content ratio of the blue color material to PG59 can be appropriately adjusted according to the desired chromaticity, and is not particularly limited . Among them, from the viewpoint of suppressing the occurrence of display defects and enhancing color reproducibility and increasing brightness, it is preferable to contain 10 to 300 parts by mass of blue color material, more preferably 20 to 200 parts by mass relative to 100 parts by mass of PG59. share.

In addition, relative to the total amount of the color material, the blue color material preferably contains 3 to 60% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass.

In the photosensitive colored resin composition for color filters according to the second aspect of the present invention, the content ratio of the yellow color material to PG59 can be adjusted appropriately according to the desired chromaticity, and is not particularly limited . Among them, from the viewpoint of suppressing the occurrence of display defects and enhancing color reproducibility and increasing brightness, it is preferable to contain 10 to 800 parts by mass of yellow color material, and more preferably 20 to 600 parts by mass relative to 100 parts by mass of PG59. share.

Furthermore, it is preferable to contain the yellow color material in 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 70% by mass relative to the total amount of the color material.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second invention, the content ratio of the yellow color material to the blue color material can be adjusted appropriately according to the desired chromaticity. Specially limited. Among them, from the viewpoint of suppressing the occurrence of display defects and increasing color reproducibility and increasing brightness, it is preferable to contain 10 to 800 parts by mass of the yellow color material, and more preferably 20 to 100 parts by mass of the blue color material. 600 Mass parts.

In the photosensitive colored resin composition for color filters of the third embodiment of the second invention, when (Y1) at least one yellow color material containing CI Pigment Yellow 185 is used, PY185 is relative to the yellow color material The total content is preferably 10-100% by mass, more preferably 20-100% by mass. PY185 series has strong coloring power, even if it contains about 10% by mass relative to the total amount of yellow color material, it still has the effect of reducing the above-mentioned P/V ratio.

Furthermore, in (Y1), if PY139 is contained in addition to PY185, it is equivalent to (Y1), but the content of PY139 is preferably 10 to 90% by mass relative to the total amount of the yellow color material, more preferably 20 to 80 quality%.

In addition, in the photosensitive colored resin composition for color filters according to the third embodiment of the second invention, (Y2) uses CI Pigment Yellow 139 as an essential component, and further contains CI Pigment Yellow 138 and CI In the case of at least two types of yellow color materials composed of pigment yellow 150 and its derivative pigments, relative to the total amount of yellow color materials, the content of PY139 is preferably 5 to 95% by mass, more preferably 10 to 90% by mass %. 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 pigments relative to the total amount of the yellow color material is preferably 5 to 95% by mass, more preferably 10 to 90% by mass .

As the above-mentioned (Y2), from the viewpoint of suppressing the occurrence of display defects and easily achieving a high-brightness and high-contrast colored layer, it is preferable to use PY139 as an essential component, and further include a pigment selected from PY150 and its derivatives At least two yellow color materials from one or more of the group. In addition, as (Y2), if PY139 and at least two yellow color materials selected from the group consisting of PY150 and its derivative pigments are combined with the above PG59 and blue color materials, the above P can be further reduced. /V ratio, suppression of developing residue, It is preferable from the viewpoint of improving the development adhesion and plate-making properties.

Among the above-mentioned combinations, from the viewpoint of enhancing brightness and easily reducing the above-mentioned P/V ratio, it is preferable to use PY139 as an essential component and further contain at least two kinds of yellow color materials containing nickel complex-containing derivative pigments of PY150.

As (Y2), when PY139 is combined with one or more selected from the group consisting of PY150 and its derivative pigments, from the viewpoint of easily achieving a high-brightness and high-contrast colored layer, it is preferably selected from PY150 The content of one or more types of pigments and its derivative pigments is more than the content of PY139, more preferably 150~700 parts by mass, and even more preferably 200~600 parts by mass relative to 100 parts by mass of PY139.

In the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the above-mentioned specific yellow color material is appropriately selected, and may be used singly or as a mixture of two or more.

In the second invention, PY185 is suitable for expanding the color reproduction area, and is preferably used for the chromaticity area of y=0.610~0.720, x=0.140~0.230, and then y=0.720~0.750 In this case, it is better to be used in the case where the chromaticity region is expressed as x=0.140~0.210.

In addition, PY139 is preferably used to display the chromaticity region of y=0.570~0.710 and x=0.180~0.265.

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

Even if it further contains green color materials other than PG59, the content ratio of the green color material containing PG59 to the total color material, and the blue color material relative to the content The content ratio of the green color material of PG59, the content ratio of the blue color material to the whole 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 whole color material are preferable. It is the content ratio of PG59 relative to the whole color material, the content ratio of blue color material to PG59, the content ratio of blue color material to the whole color material, the content ratio of yellow color material to PG59, and the yellow color material. The content ratio of the whole color material is the same.

In addition, in the second photosensitive colored resin composition for color filters of the third embodiment of the present invention, when PG7 is further contained, it is preferable to contain 5-50 relative to the total amount of the green color material containing PG59. Mass% of PG7, from the viewpoint of poor display and brightness, and the above-mentioned P/V ratio, it is more preferable to contain 5 to 45% by mass.

In addition, in the photosensitive colored resin composition for a color filter according to the third embodiment of the second aspect of the present invention, the color material may further contain a green color material and a blue color within a range that does not impair the effects of the present invention. The total content of the green color material, blue color material, and the above-mentioned specific yellow color material containing PG59 for other color materials other than the yellow color material is relative to the total color material, preferably 70-100% by mass, more preferably 80~100% by mass.

The second aspect of the photosensitive colored resin composition for color filters of the present invention is the ratio of P/V ((mass of color material components in the composition)/(mass of solid content other than the color material components in the composition) ) Is from the viewpoint of degassing or heat shrinkage, preferably 0.1 or more, more preferably 0.2 or more; From the viewpoints of excellent performance, development resistance, and effect of suppressing the occurrence of water bleeding, it is preferably 0.7 or less, more preferably 0.6 or less, and still more preferably 0.5 or less.

<Cure film of photosensitive colored resin composition for color filters>

The second aspect of the photosensitive colored resin composition for color filters of the second embodiment of the present invention is preferably that the chromaticity coordinates that can be formed in the XYZ color system of JIS Z8701 measured with a C light source are x=0.180~0.330, y=0.500~0.750 in the range of hardened film.

Among them, from the viewpoint of improving color reproducibility, the second photosensitive colored resin composition for color filters of the second embodiment of the present invention can be formed on the XYZ color of JIS Z8701 measured by the C light source The chromaticity coordinates in the system are x=0.188~0.324, y=0.550~0.750, the cured film is better, x=0.200~0.324, y=0.570~0.750, the cured film is better, x The hardened film in the range of =0.205~0.324 and y=0.580~0.750 is the best.

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

As a good blending ratio or combination of the color space that can be expressed in the range of 37≦Y, the total content of the color materials is 20-45% by mass relative to the total solid content of the photosensitive colored resin composition for color filters; 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. Among 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 thickness of the cured film here is that after the photosensitive colored resin composition for the color filter is coated, dried, exposed and cured, and then post-baked in a dust-free oven at 230°C for 30 minutes The film thickness.

The second embodiment of the photosensitive colored resin composition for a color filter of the third embodiment of the present invention is preferably capable of forming the chromaticity coordinates in the XYZ color system of JIS Z8701 measured with a C light source as x= Those with a hardened film within the range of 0.140~0.330, y=0.500~0.750.

Among them, from the viewpoint of improving color reproducibility, the second, photosensitive colored resin composition for color filters of the third embodiment of the present invention can form the XYZ color system of JIS Z8701 measured by using a C light source The chromaticity coordinates in x=0.140~0.280, y=0.570~0.730 are better for the cured film, and the cured film can be formed within the range of x=0.140~0.265, y=0.610~0.720 is more preferable. It is best to form a cured film within the range of x=0.180~0.230 and y=0.690~0.710.

The second aspect of the cured film of the photosensitive colored resin composition for the color filter of the third embodiment of the present invention has a film thickness of 2.8 μm or less and the color measured by a single pixel using a C light source in accordance with JIS Z8701 Among the chromaticity coordinates in the XYZ color system, the better one can display the color space of x=0.140~0.265, y=0.570~0.720 and the stimulus value Y is 16≦Y, and the better one 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. Furthermore, the thickness of the cured film here is that the photosensitive colored resin composition for color filters is coated, dried, exposed to light, and the polyfunctional monomer is cured, and then performed in a dust-free oven at 230°C. Film thickness after 30 minutes of post-baking.

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

In addition, as a good blending ratio or combination of the color space that can be expressed as x=0.180~0.265, y=0.570~0.710, and stimulus value Y in the range of 16≦Y, it is preferable to use the above (Y2) as the yellow color material; Relative to the total amount of color material, it is preferable that the green color material containing CI Pigment 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; relative to the total amount of color material More preferably, the green color material containing CI Pigment Green 59 is 15-60% by mass, the blue color material is 10-40% by mass, and the yellow color material is 20-60% by mass.

<Manufacturing Method of Photosensitive Colored Resin Composition for Color Filter>

The method for producing the photosensitive colored resin composition for a color filter of the second invention is not particularly limited. For example, it can be achieved by adding an alkali-soluble resin and a polyfunctional group to the color material dispersion of the second invention. The monomer, the photoinitiator, and other components as needed are mixed and obtained by using a known mixing method. Or when it contains other color materials different from PG59 as in the second embodiment or the third embodiment, use the above-mentioned dispersant to prepare PG59 color material dispersion liquid, yellow color material dispersion liquid, and then If necessary, the color material dispersion liquid of other color materials, the color material dispersion liquid containing PG59, the color material dispersion liquid containing yellow color material, and the color material dispersion liquid of other color materials, alkali-soluble resin, multifunctional The base monomer, the photoinitiator, and other components as necessary are mixed by using a known mixing means to obtain a photosensitive colored resin composition for color filters.

II-3. The second color filter related to the present invention

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

The second color filter related to the present invention, if at least one layer of the colored layer has a coloring layer formed by curing the photosensitive colored resin composition for a color filter related to the second present invention, it can become Color filters with high brightness, high contrast and excellent color reproducibility.

If the second color filter related to the present invention has a colored layer formed by curing the photosensitive colored resin composition for a color filter related to the second present invention, the other structure can be the same as the first one. The description of the color filter related to the invention is the same, so the description is omitted here.

II-4, 5. The second liquid crystal display device and organic light emitting display device related to the present invention

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

The second organic light emitting display device related to the present invention is characterized by having the above-mentioned second color filter related to the present invention and an organic light-emitting body.

In the second aspect of the present invention, by using the second color filter, it is possible to provide a liquid crystal display device with high brightness and excellent color reproducibility and an organic light emitting display device.

If the second liquid crystal display device and organic light emitting display device related to the present invention are provided with the second color filter related to the present invention, other configurations are possible The description of the liquid crystal display device and the organic light emitting display device related to the above-mentioned first invention is the same, so the description is omitted here.

(Example)

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

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

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

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

The weight average molecular weight (Mw) of the block copolymer before the salt formation is obtained by using GPC (Gel Permeation Chromatography) as a standard polystyrene conversion value in accordance with the measurement method of the present invention described above.

In addition, the glass transition temperature (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 calculated by the following formula. As a result, it was found that the block copolymer A-1 was 37°C (DSC measurement value 38°C), the block copolymer A-26 was 64°C (DSC measurement value 66°C), and the block copolymer A-22 was 0. The temperature of the block copolymer A-24 is 20°C (the value measured by DSC is 2°C), and it is almost the same as the value measured by DSC.

1/Tg=Σ(Xi/Tgi)

Here, the block copolymerization system is set to copolymerize n monomer components of i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, Σ is the sum from i-1 to n. In addition, the value of the homopolymer glass transition temperature (Tgi) of each monomer is the value of Polymer Handbook (3rd Edition) (by J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)). Specifically, the value (Tgi) of the homopolymer glass transition temperature (Tgi) of each monomer used in the Example and the comparative example is as follows.

Methacrylic acid (MAA): 185°C

2-Hydroxyethyl methacrylate (HEMA): 55°C

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

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

Dimethylaminopropyl methacrylamide (DMAPMA): 96°C

Methoxy polyethylene glycol monomethacrylate (trade name: PME-100, manufactured by NOF Corporation, BLEMMER-PME-100, repeating number of ethyleneoxy groups = 2): -26°C

Methoxy polyethylene glycol monomethacrylate (trade name: PME-200, manufactured by NOF Corporation, BLEMMER-PME-200, repeating number of ethyleneoxy groups = 4): -59°C

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

Example I series: the first invention

(Synthesis Example 1: Production of block copolymer A-1)

In a 500 mL round bottom four-necked flask equipped with a cooling tube, an addition funnel, an air inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to fully perform nitrogen substitution. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. The monomers for the B block are 0.37 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.6 parts by mass of 2-ethylhexyl methacrylate (EHMA), and 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 stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a solid content 30% by mass solution. 32.5 parts by mass of water was added, the temperature was raised to 100° C., and the reaction was conducted for 7 hours, and the constituent unit derived from EEMA was deprotected to produce a constituent unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution was re-precipitated in hexane, and purified by filtration and vacuum drying to obtain a composition containing the A block containing the structural unit represented by the general formula (I) and the composition derived from the carboxyl-containing monomer It is a block copolymer A-1 (acid value 1mgKOH/g, Tg38°C) which is a unit and has a solvent-philic B block. The block copolymer A-1 thus obtained was confirmed by GPC (Gel Permeation Chromatography), and the weight average molecular weight Mw was 7,600. In addition, the amine value is 96 mgKOH/g.

(Synthesis examples 2~3: Synthesis of block copolymers A-2~A-3)

In Synthesis Example 1, except for changing the content shown in Table 1, the same procedure as Synthesis Example 1 was performed to synthesize block copolymers A-2 to A-3. In Synthesis Example 2, 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used; in Synthesis Example 3, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. The acid value, Tg, and amine value of the block copolymer obtained 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 the salt formation of the salt type block copolymer A-4 is the same as the block copolymer A-2 series).

In a 100 mL round pill flask, 10.0 parts by mass of the block copolymer A-2 was dissolved in 41.93 parts by mass of PGMEA, and 0.48 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry), which belongs to the compound represented by the above general formula (3), was added (Compared to the compound represented by the general formula (3), the DMMA unit of block copolymer A-2 is 1 mol, which is 0.20 mol). Stir at a reaction temperature of 30°C for 20 hours to obtain a salt with a solid content of 20% by mass 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 specific amine value after salt formation is calculated as follows.

Put 9 mass parts of salt-type block copolymer A-4 (solid after reprecipitation) and 91 mass parts for chloroform-D1NMR into 1 g of the NMR sample tube, and use a nuclear magnetic resonance device (manufactured by JEOL, FT). NMR, JNM-AL400), the 13C-NMR spectrum was measured under the conditions of room temperature and 10,000 cumulative times. In the obtained spectrum data, the nitrogen portion (amine group) at the end is based on the ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom that has not undergone salt formation and the peak of the carbon atom adjacent to the nitrogen atom formed by the salt, Calculate the ratio of the number of amine groups formed by the salt to the total number of amine groups, and confirm that it is different from the theoretical salt formation ratio (total phenylphosphonic acid is the nitrogen at the end of the DMMA of the block copolymer A-2 Site formation of salt).

From the amine value of 95 mgKOH/g before the salt formation minus the 0.20 mole part of the amine value of the DMMA unit (19 mgKOH/g), the amine value after the salt formation was calculated to be 76 mgKOH/g. Table 1 shows the Tg of the block copolymers before and after the salt formation.

(Synthesis examples 5~10: Synthesis of salt type block copolymers A-5~A-10)

In Synthesis Example 4, except that the salt-forming compound was changed to the compound and the amount shown in Table 1, the same procedure was performed as in Synthesis Example 4 to obtain solutions of salt-type block copolymers A-5 to A-10.

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

Furthermore, 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 that shown in the general formula (I) The nitrogen site (DMMA) of the unit is represented by 1 mol.

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

In Synthesis Example 1, except for changing the content shown in Table 1, the same procedure was performed as in Synthesis Example 1, and the block copolymers A-11 to A-12 used in the comparative examples were synthesized. Table 1 shows the acid value, Tg, and amine value of the obtained block copolymer.

(Synthesis Example 13: Production of block copolymer A-13)

In a 500 mL round bottom four-necked flask equipped with a cooling tube, addition funnel, nitrogen gas inlet, mechanical stirrer, and digital thermometer, add tetrahydrofuran through the addition funnel 250 parts by mass of pyran (THF) and 5.81 parts by mass of dimethyl ketene methyl trimethylsilyl acetal as the starting agent, and nitrogen substitution was sufficiently carried out. Inject 0.5 parts by mass of 1 mol/L acetonitrile solution of catalyst tetrabutylammonium o-chlorobenzoic acid into a syringe, and use an addition funnel to add 18.7 parts by mass of HEMA and 12.8 parts of EHMA for the B block monomer Parts, 13.7 parts by mass of BMA, 9.5 parts by mass of BzMA, and 19.5 parts by mass of MMA 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, which is a monomer for the A block, was dropped over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was re-precipitated in hexane and purified by filtration and vacuum drying to obtain the A block containing the structural unit represented by the general formula (I), and the B block containing solvent-philicity. Block copolymer A-13 (Tg37°C). The block copolymer A-13 thus obtained was confirmed by GPC (Gel Permeation Chromatography), and the weight average molecular weight Mw was 7320. In addition, the amine value was 92 mgKOH/g.

(Synthesis examples 14~17: Synthesis of salt type block copolymers A-14~A-17)

In Synthesis Example 4, except for the block copolymer A-13 of Synthesis Example 13 (salt-type block copolymer A-14 to A-17 before the salt is formed, the block copolymer and the block copolymer A-13 Same system) As the block copolymer before salt formation, the salt-forming compound was changed to the compound and the amount shown in Table 1, and the rest was the same as in Synthesis Example 4 to obtain salt-type block copolymers A-14 to A-17 Solution.

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

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

In Synthesis Example 1, except for changing the content shown in Table 2 or Table 3, the same procedure as Synthesis Example 1 was performed to synthesize the block copolymers A-18 to A-34 used in the Examples or Comparative Examples. The acid value, Tg, and amine value of the obtained block copolymer are shown in Table 2 or Table 3.

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

In Synthesis Example 4, except for the block copolymer A-33 of Synthesis Example 33 (salt type block copolymer A-35~A-37 before the salt is formed, the block copolymer and the block copolymer A-33 Same system) As the block copolymer before salt formation, the salt-forming compound was changed to the compound and the amount shown in Table 3, and the rest was the same as Synthesis Example 4 to obtain salt-type block copolymers A-35 to A-37 Solution.

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

(Synthesis Examples 38~40: Synthesis of block copolymers A-38~A-40)

With reference to Synthesis Examples 1, 2 and 5 (B-1, B-2, and B-5) of Patent Document 2 and proceeding in the same manner, the block copolymers A-38 to A-40 used in the comparative examples were synthesized respectively. Table 4 shows the acid value, Tg, and amine value of the obtained block copolymer.

[Table 1]

[Table 2]

[table 3]

[Table 4]

Synthesis Example 41 (Synthesis of Alkali-soluble Resin A Solution)

Fill the polymerization tank with 300 parts by mass of PGMEA, and after raising the temperature to 100°C in a nitrogen environment, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA) and 54 parts by mass of MMA The amount, 36 parts by mass of methacrylic acid (MAA), 6 parts by mass of PERBUTYLO (manufactured by NOF Corporation), and 2 parts by mass of the chain transfer agent (n-dodecyl mercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction was continued at 100°C, and 2 hours after the completion of the dropping of the above-mentioned main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization.

Next, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound. After the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added and the addition reaction was performed at 110°C. 15 After hours, an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass) was obtained.

Furthermore, the above-mentioned method for measuring the weight average molecular weight is to use polystyrene as the standard substance and THF as the eluent to determine the weight average molecular weight by Shodex GPC system-21H (Shodex GPC system-21H). In addition, the method for measuring the acid value is measured in accordance with JIS K 0070.

(Example 1)

(1) Manufacturing of color material dispersion G-1

Obtained from 3.25 parts by mass of the block copolymer A-1 of Synthesis Example 1 as a dispersant, 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 Put 16.25 parts by mass of alkali-soluble resin A solution, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0mm into the beauty milk bottle, and shake with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour As a preliminary disintegration, the zirconia beads with a diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads with a diameter of 0.1mm were added, and the same was carried out with a pigment shaker for 4 hours as a formal disintegration to obtain a color material dispersion G -1.

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

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF JAPAN(股)製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF JAPAN製)0.04質量份、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名IRGACURE OXE02，BASF JAPAN(股)製)0.02質量份、氟系界面活性劑(商品名MEGAFACE R-08MH，DIC(股)製)0.07質量份、PGMEA7.14質量份，得到彩色濾光片用感光性著色樹脂組成物G-1。 Add 11.40 parts by mass of the color material dispersion G-1 obtained in (1) above, 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, Toagosei Co., Ltd.) Company made) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-

Phytopropan-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF JAPAN Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alkynylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF JAPAN) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl )-9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name IRGACURE OXE02, manufactured by BASF JAPAN (stock)) 0.02 parts by mass, fluorine-based surfactant ( Trade name MEGAFACE R-08MH, manufactured by DIC Co., Ltd.) 0.07 parts by mass and 7.14 parts by mass of PGMEA to obtain photosensitive colored resin composition G-1 for color filters.

(Examples 2~26)

(1) Manufacturing of color material dispersion G-2~G-26

In (1) of Example 1, except for the substituted block copolymer A-1, as shown in Tables 5 to 7, respectively, depending on the way that the solid content becomes the same mass part as the block copolymer A-1 Use the block copolymers A-2~A-3 of synthesis examples 2~3, the salt-type block copolymers A-4~A-10 solutions of synthesis examples 4-10, and the block copolymers of synthesis examples 18-21 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, adjust PGMEA so that the total is 100 parts by mass Except for the amount, the rest was performed in the same manner as (1) of Example 1 to obtain color material dispersion liquids G-2 to G-26. (2) Production of photosensitive colored resin composition G-2~G-26 for color filters

In Example 1 (2), except that instead of the color material dispersion G-1, the above-mentioned color material dispersions G-2 to G-26 were used, respectively, the rest was performed in the same manner as in Example 1 (2) to obtain a color Photosensitive colored resin compositions G-2 to G-26 for filters.

(Example 35)

(1) Manufacturing of color material dispersion G-27

Obtained from 3.25 parts by mass of block copolymer A-2 of Synthesis Example 2 as a dispersant, CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) as a color material, 13 parts by mass, and Synthesis Example 41 Put 16.25 parts by mass of alkali-soluble resin A solution, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0mm into the beauty milk bottle, and shake with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour As a preliminary disintegration, the zirconia beads with a diameter of 2.0mm were taken out, 200 parts by mass of zirconia beads with a diameter of 0.1mm were added, and the same was carried out with a pigment shaker for 4 hours as a formal disintegration to obtain a color material dispersion G -27.

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

In Example 1 (2), except that instead of the color material dispersion G-1, the above color material dispersion G-27 was used, the rest was carried out in the same manner as in Example 1 (2) to obtain a color filter. Photosensitive colored resin composition G-27.

(Examples 36~38)

(1) Manufacturing of color material dispersion G-28~G-30

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

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

In (2) of Example 35, except for replacing the color material dispersion G-27, and using the above-mentioned color material dispersions G-28 to G-30, the rest was performed in the same manner as in (2) of Example 35 to obtain Photosensitive colored resin composition G-28 to G-30 for color filters.

(Example 39)

In (1) of Example 1, in addition to replacing CI Pigment Green 58 (PG58) as the color material, CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) was used instead of the dispersant. The block copolymer A-1 of Synthesis Example 1 was used except that the block copolymer A-2 of Synthesis Example 2 was used, and the rest was carried out in the same manner as in Example 1 (1) to obtain a color material dispersion liquid G-31.

(2) Manufacturing of photosensitive colored resin composition G-31 for color filters

In Example 1 (2), except that instead of the color material dispersion G-1, the above-mentioned color material dispersion G-31 was used, the rest was carried out in the same manner as in Example 1 (2) to obtain a color filter. Photosensitive colored resin composition G-31.

(Examples 40~42)

(1) Manufacturing of color material dispersion G-32~G-34

In (1) of Example 39, except for the substituted block copolymer A-2, respectively, as As shown in Table 8, the salt-type block copolymer A-8 solution of Synthesis Example 8 and the block copolymer A- of Synthesis Example 33 were used so that the solid content became the same mass part as 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 so that the total amount was 100 parts by mass, the rest was performed in the same manner as in Example 39 (1) to obtain color material dispersion G-32 ~G-34.

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

In (2) of Example 39, except that instead of color material dispersion G-31, the above-mentioned color material dispersions G-32 to G-34 were used, the rest was carried out in the same manner as (2) of Example 39 to obtain a color Photosensitive colored resin composition G-32 to G-34 for filters.

(Comparative Examples 1~14)

(1) Manufacturing of comparative color material dispersion G-1~G14

In (1) of Example 1, except for the substituted block copolymer A-1, as shown in Tables 5 to 7, respectively, depending on the way that the solid content becomes the same mass part as the block copolymer A-1 Use the block copolymers A-11~A-13 of synthesis examples 11~13, the salt-type block copolymers A-14~A-17 solutions of synthesis examples 14-17, and the block copolymers of synthesis examples 22-25 The solution of the combination A-22~A-25 and the block copolymers A-38~A-40 of the synthesis examples 38~40, except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, the rest were the same as in Example 1 (1) The same was performed to obtain comparative color material dispersion liquids G-1 to G-14.

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

In Example 1 (2), except for replacing the color material dispersion G-1, and using the above-mentioned comparative color material dispersions G-1 to G-11, the rest was performed in the same manner as in Example 1 (2). Photosensitive colored resin compositions G-1 to G-14 for comparative color filters were obtained.

(Example 27)

(1) Manufacturing of color material dispersion R-1

The block copolymer A-1 of Synthesis Example 1 as a dispersant was 3.25 parts by mass, CI Pigment Red 177 (PR177) 6.5 parts by mass, CI Pigment Red 254 (PR254) 6.5 parts by mass, and Synthesis Example 41 as a pigment 16.25 parts by mass of alkali-soluble resin A solution, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0mm are placed in the beauty milk bottle, and shaken for 1 hour with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) Preliminary disintegration, and then take out the zirconia beads with a diameter of 2.0mm, add 200 parts by mass of the zirconia beads with a diameter of 0.1mm, and disperse for 4 hours with a pigment shaker as the formal disintegration to obtain a color material dispersion R- 1.

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

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF JAPAN(股)製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF JAPAN製)0.04質量份、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名IRGACURE OXE02，BASF JAPAN(股)製)0.02質量份、氟系界面活性劑(商品名MEGAFACE R-08MH，DIC(股)製)0.07質量份、PGMEA7.14質量份，得到彩色濾光片用感光性著色樹脂組成物R-1。 Add 11.40 parts by mass of the color material dispersion R-1 obtained in (1) above, 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, Toagosei Co., Ltd.) Company made) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-

Phytopropan-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF JAPAN Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alkynylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF JAPAN) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl )-9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name IRGACURE OXE02, manufactured by BASF JAPAN (stock)) 0.02 parts by mass, fluorine-based surfactant ( Trade name MEGAFACE R-08MH, manufactured by DIC Corporation) 0.07 parts by mass and 7.14 parts by mass of PGMEA, to obtain photosensitive colored resin composition R-1 for color filters.

(Example 28~30)

(1) Manufacturing of color material dispersion R-2~R-4

In Example 27 (1), except for the substituted block copolymer A-1, as shown in Table 9, the synthesis examples were used in such a way that the solid content becomes the same mass part as the block copolymer A-1. 27, 3, and 4 block copolymers A-27, A-3 and salt-type block copolymer A-4 solutions, except that the amount of PGMEA was adjusted to a total of 100 parts by mass, the rest were the same as those of Example 27 (1 ) In the same manner, color material dispersion liquids R-2 to R-4 are obtained.

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

In (2) of Example 27, except that the color material dispersion liquid R-1 was substituted, and the above-mentioned color material dispersion liquids R-2 to R-4 were used respectively, the rest was carried out in the same manner as in (2) of Example 27 to obtain Photosensitive colored resin compositions R-2 to R-4 for color filters.

(Comparative Examples 15-18)

(1) Manufacturing of comparative color material dispersion R-1~R-4

In Example 27 (1), except for the substituted block copolymer A-1, as shown in Table 9, the solid content becomes the same mass part as the block copolymer A-1. The block copolymers A-11, A-13, A-24, and A-25 of Examples 11, 13, 24, and 25, except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, the rest were the same as those of Example 27 (1 ) In the same manner, comparative color material dispersion liquids R-1 to R-4 are obtained.

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

In (2) of Example 27, except for replacing the color material dispersion R-1, and using the above-mentioned comparative color material dispersions R-1 to R-4, the rest was performed in the same manner as in (2) of Example 27. The photosensitive colored resin compositions R-1 to R-4 for comparative color filters were obtained.

(Example 31)

(1) Manufacturing of color material dispersion B-1

Synthesize 3.25 parts by mass of block copolymer A-1 of Synthesis Example 1 as a dispersant, CI Pigment Blue 15:6 (PB15:6) 10.4 parts by mass, and CI Pigment Violet 23 (PV23) 2.6 parts by mass as pigments. The 16.25 parts by mass of alkali-soluble resin A solution, 67.5 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm obtained in Example 41 were placed in a beauty milk bottle, and a pigment oscillator (manufactured by Asada Iron Works Co., Ltd.) Shake for 1 hour as a preliminary disintegration, then take out the zirconia beads with a diameter of 2.0mm, add 200 parts by mass of the zirconia beads with a diameter of 0.1mm, and disperse in the same way with a pigment shaker for 4 hours as a formal disintegration to obtain a color material Dispersion B-1.

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

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF JAPAN(股)製)0.15質量份、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF JAPAN製)0.07質量份、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名IRGACURE OXE02，BASF JAPAN(股)製)0.03質量份、氟系界面活性劑(商品名MEGAFACE R-08MH，DIC(股)製)0.07質量份、PGMEA9.06質量份，得到彩色濾光片用感光性著色樹脂組成物 B-1。 Add 8.59 parts by mass of the color material dispersion B-1 obtained in (1) above, 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, Toagosei Co., Ltd.) Company made) 0.98 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-

Linylpropane-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF JAPAN Co., Ltd.) 0.15 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alkynylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF JAPAN) 0.07 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl )-9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name IRGACURE OXE02, manufactured by BASF JAPAN (stock)) 0.03 parts by mass, fluorine-based surfactant ( Trade name MEGAFACE R-08MH, manufactured by DIC Corporation) 0.07 parts by mass and 9.06 parts by mass of PGMEA, to obtain a photosensitive colored resin composition B-1 for color filters.

(Examples 32~34)

(1) Manufacturing of color material dispersion B-2~B-4

In Example 31 (1), except for the substituted block copolymer A-1, as shown in Table 10, the synthesis examples were used in such a way that the solid content became the same mass part as the block copolymer A-1. 27, 3, and 4 block copolymers A-27, A-3 and salt-type block copolymer A-4 solutions, except that the amount of PGMEA was adjusted to a total of 100 parts by mass, and the rest were the same as those of Example 31 (1 ) In the same manner, color material dispersion liquids B-2 to B-4 are obtained.

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

In (2) of Example 31, except for replacing the color material dispersion B-1, and using the above-mentioned color material dispersions B-2 to B-4, the rest was performed in the same manner as in (2) of Example 31 to obtain Photosensitive colored resin compositions B-2 to B-4 for color filters.

(Comparative Examples 19-22)

(1) Manufacturing of comparative color material dispersions B-1~B-4

In Example 31 (1), except for the substituted block copolymer A-1, as shown in Table 10, the synthesis examples were used in such a way that the solid content became the same mass part as the block copolymer A-1. 11, 13, 24, and 25 block copolymers A-11, A-13, A-24 and A-25, except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, the rest were the same as in Example 31 (1) The same was performed to obtain comparative color material dispersion liquids B-1 to B-4.

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

In (2) of Example 31, except for replacing color material dispersion B-1, and using the above-mentioned comparative color material dispersions B-1 to B-4, the rest was the same as in Example 31 (2). Then, photosensitive colored resin compositions B-1 to B-4 for comparative color filters were obtained.

[Evaluation method]

<Evaluation of Dispersibility of Color Material Dispersion>

For the color material dispersions obtained in the Examples and Comparative Examples, the viscosity immediately after preparation and after storage at 25°C for 30 days were measured, and the viscosity change rate was calculated from the viscosity before and after storage, and the viscosity stability was evaluated. In the viscosity measurement system, a vibrating viscometer was used to measure the viscosity at 25.0±0.5°C. The results are shown in Tables 5-10.

(Evaluation criteria for dispersion stability)

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

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

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

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

However, it is a value when the color material is 13% by mass relative to the total mass of the solvent containing the color material dispersion liquid.

Although the color material dispersion liquid whose evaluation result is C can be used for practical use, if the evaluation result is B, the color material dispersion liquid is more favorable, and if the evaluation result is A, the dispersion stability of the color material dispersion liquid is excellent.

<Optical performance evaluation, comparative evaluation>

The photosensitive colored resin compositions for color filters obtained in the Examples and Comparative Examples were applied to a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm and a thickness of 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 colored layer. For this colored layer, an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of ^{60 mJ/cm 2.}

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 resulting colored substrate were measured using a comparison measuring device CT-1B manufactured by Kosaka Electric and a microscope OSP-SP200 manufactured by Olympus. Degree (x, y), brightness (Y). The results are shown in Tables 5-10.

(Comparative evaluation criteria)

A: Green exceeds 7000, Red exceeds 5000, Blue exceeds 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, the Green of Examples 1 to 26 and Comparative Examples 1 to 11 under C light source is y=0.570, the Green of Examples 35 to 38 is y=0.420, and the Green of Examples 39 to 42 is y=0.480 , Red of Examples 27-30 and Comparative Examples 12-15 is x=0.650, and Blue of Examples 31-34 and Comparative Examples 16-19 is the value when y=0.107.

<Evaluation of developing residue>

The photosensitive colored resin compositions for color filters obtained in the Examples and Comparative Examples were applied to a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm and a thickness of 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 with a thickness of 2.5 μm. The above-mentioned glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkali developer. After visually observing the unexposed part (50mm×50mm) of the glass substrate after the colored layer is formed, wipe it with a lens cleaning cloth containing ethanol (Toraysee MK cleaning cloth, trade name), and observe the lens visually The degree of coloration of the cleaning cloth. The results are shown in Tables 5-10.

(Evaluation criteria for developing residue)

A: No development residue is visually confirmed, and the lens cleaning cloth is completely uncolored

B: No development residue was confirmed visually, but slight staining of the lens cleaning cloth was confirmed

C: A slight development residue is visually confirmed, and the lens cleaning cloth is slightly colored

D: A slight development residue is visually confirmed, and the coloring of the lens cleaning cloth is confirmed

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

If the development residue evaluation standard is A, B, or C, it is evaluated that the occurrence of development residue is sufficiently suppressed, and it can be used practically without any problems.

<Evaluation of developing adhesion>

The photosensitive colored resin compositions for color filters obtained in the Examples and Comparative Examples were applied to a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm and a thickness of 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 with a thickness of 2.5 μm. For this colored layer, an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of ^{60 mJ/cm 2 through a mask having a mask opening width of 2 to 80 μm.} The above-mentioned glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkali developer. Observe the developed substrate with an optical microscope to observe whether there is a colored layer relative to the line width of the mask opening. The results are shown in Tables 5-10.

(Evaluation Criteria for Developing Adhesiveness)

A: The colored layer is observed in the part where the line width of the mask opening is less than 10μm

B: Coloring is observed in the part where the line width of the mask opening is 10μm or more and less than 20μm Floor

C: The colored layer is observed in the part where the line width of the mask opening is 20μm or more but less than 50μm

D: The colored layer is observed in the part where the line width of the mask opening is 50μm or more but less than 80μm

E: No colored layer is observed in the part of the mask opening line width below 80μm

If the evaluation result is C, the photosensitive colored resin composition for color filters can be used for practical purposes; but if the evaluation result is B, the photosensitive colored resin composition for color filters is suitable for more refined applications ; If the evaluation result is A, the photosensitive colored resin composition for color filters can be applied to more high-definition occasions.

<Evaluation of solvent resolubility>

The front end of a glass substrate with a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for color filters obtained in the Examples and Comparative Examples, and coated on the portion of the glass substrate with a length of 1 cm. The pulled up glass substrate is placed in a constant temperature and humidity machine so that the glass surface is horizontal, and it is dried under the conditions of a temperature of 23° C., a humidity of 80% RH and 30 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. The re-dissolution state of the dried coating film at this time was visually judged and evaluated. The results are shown in Tables 5-10.

(Evaluation criteria for solvent resolubility)

A: The dried coating film is completely dissolved

B: A flake with a dry coating film produced in the solvent, and the flake is slightly dissolved

C: Thin slices of dried coating film produced in the solvent, the solution is colored

D: Flake of dry coating film is produced in the solvent, and the solution is not colored

E: No dry film is produced in the solvent, and the solution is not colored

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

[table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Result integration]

It is clear from the results of Table 1 to Table 10 that the use of: A block containing the structural unit represented by the above general formula (I) and B containing the structural unit derived from the carboxyl-containing monomer and having solvophilicity A block copolymer; and at least a part of the nitrogen site of the structural unit represented by the general formula (I) of the block copolymer, and selected from the following general formulas (1) to (3) At least one of the salt-type block copolymers composed of one or more compounds forming a salt, and the acid value of the dispersant is 1-18 mgKOH/g, and the glass transition temperature of the dispersant is 30°C or higher. The color material dispersion liquids of Examples 1 to 42 of the dispersant have superior color material dispersion. In addition, the photosensitive colored resin composition for color filters of Examples 1 to 42 prepared using the color material dispersions of Examples 1 to 42 has excellent color material dispersion stability, suppresses the occurrence of development residues, and develops Excellent adhesion and solvent re-solubility.

Among them, Examples 4 to 10 and 24 to 26, 30, 34, 36, 38, 40, and 42 using the above-mentioned salt-type block copolymers have particularly excellent color material dispersibility, and the resulting colored layer has excellent contrast.

On the other hand, although the glass transition temperature of the dispersant is above 30°C, the comparative examples 1, 2, 12-14, 15 and 19, whose acid value is higher than the specific value in this case, are due to poor developing adhesion and higher acid value. The solvent re-solubility of Comparative Examples 2 and 12 to 14 also deteriorated. On the other hand, although the glass transition temperature of the dispersant was 30° C. or higher, the comparative examples 3 to 7, 16, and 20 in which the acid value was lower than the specific value of this case were all poor in evaluation of the development residue. Although the acid value of the dispersant is the specific value of this case, the glass transition temperature of the dispersant is lower than the specific value of this case in Comparative Examples 8-10, 17 and 21, because of poor developing adhesion. In addition, Comparative Examples 11, 18, and 22 in which the glass transition temperature of the dispersant is 23°C and the acid value is higher than the specific value in this case are developed with dense viscosity Difference.

Example II Series: The second embodiment of the first embodiment of the present invention

(Synthesis Example II-1: Preparation of Dispersant a)

After drying a 500 ml four-necked separating flask under reduced pressure, Ar (argon) substitution was performed.

0.2g。於其中使用滴下漏斗，將甲基丙烯酸甲酯(MMA)36.7g歷時45分鐘滴下。由於反應進行時發熱，故藉由冰浴將溫度保持為未滿40℃。1小時後，將甲基丙烯酸二甲基胺基乙酯(DMMA)13.3g歷時15分鐘滴下。反應1小時後，加入甲醇5g使反應停止。將溶劑減壓去除，得到嵌段共聚合體II-A1。藉由GPC測定(NMP LiBr10mM)求得的質量平均分子量為6,000，胺價為95mgKOH/g。 While blowing Ar, add 100g of dehydrated THF, 2.0g of methyltrimethylsilyldimethylketene acetal, 0.15ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoic acid (TBACB),

0.2g. Using a dropping funnel, 36.7 g of methyl methacrylate (MMA) was dropped over 45 minutes. Since heat is generated during the reaction, the temperature is 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 obtain block copolymer II-A1. The mass average molecular weight determined by GPC measurement (NMP LiBr10mM) is 6,000, and the amine value is 95mgKOH/g.

In a 100 mL round pill flask, 29.35 parts by mass of 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.) 3.17 belonging to the compound represented by the above general formula (3) was added. Parts by mass (1 mol of DMMA unit of block copolymer 1 relative to the compound represented by the above general formula (3), which is 0.20 mol), stirred at the reaction temperature of 30°C for 20 hours to obtain salt type block copolymer II -A1 (dispersant a). The amine value after salt formation is specifically calculated as follows.

Put 9 mass parts of salt-type block copolymer II-A1 (solids after reprecipitation) and 91 mass parts for chloroform-D1NMR into 1 g of the solution in the NMR sample tube. Use a nuclear magnetic resonance device (manufactured by JEOL, FT). NMR, JNM-AL400), the 13C-NMR spectrum was measured under the conditions of room temperature and 10,000 cumulative times. In the obtained spectral data, at the end At the end of the nitrogen site (amine group), the amine formed by the salt is calculated by the ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom that has not undergone salt formation and the peak of the carbon atom adjacent to the nitrogen atom formed by the salt The ratio of the number of groups 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 site at the end of the DMMA of the block copolymer II-A1).

From the amine value of 95 mgKOH/g before salt formation minus the 0.40 mole part of the amine value of the DMMA unit (38 mgKOH/g), the amine value after salt formation was calculated to be 57 mgKOH/g. Table 11 shows the Tg of the block copolymer before and after the salt formation.

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

The same procedure as the salt-type block copolymer A-8 of Synthesis Example 8 of the Example I series was carried out to obtain a solution of the salt-type block copolymer II-A2 (dispersant b). The acid value of the block copolymer after salt formation is the same as that of the block copolymer before salt formation 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)

After drying a 500 ml four-necked separating flask under reduced pressure, Ar (argon) substitution was performed.

0.2g。於其中使用滴下漏斗，將甲基丙烯酸甲酯33g歷時45分鐘滴下。由於反應進行時發熱，故藉由冰浴將溫度保持為未滿40℃。1小時後，將甲基丙烯酸二甲基胺基乙酯17g歷時15分鐘滴下。反應1小時後，加入甲醇5g使反應停止。將溶劑減壓去除，得到嵌段共聚合體II-A3。藉由GPC測定(NMP LiBr10mM) 求得的質量平均分子量為6,000，胺價為120mgKOH/g。 While blowing Ar, add 100g of dehydrated THF, 2.0g of methyltrimethylsilyldimethylketene acetal, 0.15ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoic acid (TBACB),

0.2g. Using a dropping funnel, 33 g of methyl methacrylate was dropped over 45 minutes. Since heat is generated during the reaction, the temperature is 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 obtain block copolymer II-A3. The mass average molecular weight determined by GPC measurement (NMP LiBr10mM) is 6,000, and the amine value is 120mgKOH/g.

In a 100 mL round pill flask, 24.15 parts by mass of PGMEA was dissolved in 24.15 parts by mass of block copolymer II-A3, and 3.5 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry), which belongs to the compound represented by the above general formula (3) (Relative to the compound represented by the above general formula (3), which is 1 mol of DMMA unit of block copolymer II-A3, which is 0.20 mol), 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 specific system of the amine value after salt formation was 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 for changing the content shown in Table 11, the rest was performed in the same manner as Synthesis Example II-2 to synthesize salt-forming pre-block copolymer II-A4 and salt-type block copolymer (dispersant d) Solution. In Synthesis Example II-4, 4.6 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used. Table 11 shows the acid value, Tg, and amine value of the obtained salt-formed block copolymer and salt type block copolymer.

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

The salt formation pre-block copolymer II-A2 (acid value 8 mgKOH/g, Tg 38°C) of Synthesis Example II-2 was carried out in the same manner to synthesize block copolymer II-A5 (dispersant e).

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

In Synthesis Example II-5, except for changing the monomers and contents shown in Table 11, the rest was performed in the same manner as Synthesis Example II-5 to synthesize block copolymer II-A6 (dispersant f) and Block copolymer II-A7 (dispersant g). The acid value, Tg, and amine value of the block copolymer obtained are shown in Table 11.

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

In Synthesis Example II-2, except for changing to the monomers and content shown in Table 11, the same procedure was performed as in Synthesis Example II-2, and the salt was synthesized to form the pre-block copolymer II-A8. This salt was used to form the pre-block copolymer II-A8, except that the salt-forming compound was changed to the amount shown in Table 11, and the rest was carried out in the same manner as in Synthesis Example II-2 to obtain the salt-type block copolymer II-A8 (dispersant h ) Solution. Table 11 shows the acid value, Tg, and amine value of the obtained salt-formed block copolymer and salt type block copolymer.

(Synthesis Example II-9: Synthesis of Alkali-soluble Resin A Solution)

In a polymerization tank containing 150 parts by mass of PGMEA, 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 the dropping, it was heated at 100°C for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution is 7000.

Next, add 20 parts by mass of GMA, 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol to the obtained polymer solution, and heat at 110°C for 10 hours to perform the carboxylic acid of main chain methacrylic acid. The reaction with the epoxy group of glycidyl methacrylate. During the reaction, in order to prevent the polymerization of glycidyl methacrylate, air bubbling was performed in the reaction solution. Furthermore, the reaction can be tracked by measuring the acid value of the solution. The obtained alkali-soluble resin A solution is a resin formed by the copolymerization of BzMA, MMA, and MAA, using GMA in the main chain and introducing the side chain of the ethylenic double bond. It has a solid content of 40% by mass and an acid value of 74mgKOH/ g, those with a weight average molecular weight of 12,000.

[Table 11]

The abbreviations in the table are as follows.

PME-200: Methoxy polyethylene glycol monomethacrylate (trade name: PME-200, manufactured by NOF Corporation, BLEMMER-PME-200, repeating number of ethyleneoxy groups=4)

DMAPMA: Dimethylaminopropyl methacrylamide

(Reference example II-1)

(1) Manufacturing of color material dispersion II-G1

6.18 parts by mass of the dispersant a solution of Synthesis Example II-1 as a dispersant, 13.00 parts by mass of CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) as a color material, and 13.00 parts by mass of Synthesis Example 9 Put 14.63 parts by mass of alkali-soluble resin A solution, 66.19 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0mm into the beauty milk bottle, and shake it with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour. Preliminarily disintegrate, then take out the zirconia beads with a diameter of 2.0mm, add 200 parts by mass of the zirconia beads with a diameter of 0.1mm, and disperse for 4 hours with a pigment shaker as the formal disintegration to obtain a color material dispersion II- G1.

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

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF(股)製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF 製)0.04質量份、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名ADEKA ARKLS NCI-831，ADEKA公司製)0.02質量份、氟系界面活性劑(商品名MEGAFACE F559，DIC(股)製)0.07質量份、PGMEA7.14質量份，得到彩色濾光片用感光性著色樹脂組成物II-G1。 Add 11.40 parts by mass of the color material dispersion 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 Synthetic ( (Stock) Company) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-

Hydroxypropane-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alolinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) -9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (commodity Name MEGAFACE F559, manufactured by DIC Corporation) 0.07 parts by mass and 7.14 parts by mass of PGMEA, to obtain a photosensitive colored resin composition II-G1 for color filters.

(3) Formation of colored layer

The photosensitive colored resin composition II-G1 obtained in (2) above was applied to a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm and 100 mm × 100 mm, using a spin coater. After coating, use a heating plate to dry at 80°C for 3 minutes, use an ultra-high pressure mercury lamp to irradiate 60mJ/cm ² of ultraviolet rays, and then post-bake in a dust-free oven at 230°C for 30 minutes. Under C light source, y=0.4 , Adjust the film thickness with the chromaticity of x=0.2 to form the colored layer II-G1.

(Reference example II-2~II-4, Example II-1~II-6, Comparative example II-C1~II-C4)

(1) Manufacturing of color material dispersion II-G2~II-G10, II-CG1~II-CG4

In (1) of Reference Example II-1, except that as shown in Table 12, instead of dispersant a solution, the type and amount of dispersant used were changed to make the solid content the same parts by mass. In the comparative example, it was changed. For some color materials, except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, the rest was performed in the same manner as (1) of Reference Example II-1 to obtain color material dispersion liquids II-G2~II-G10, II-CG1~II- CG4.

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

In Reference Examples II-2~II-4, Examples II-1~II-6, and Comparative Examples II-C1~II-C4, except for replacing the color material dispersion in (2) of Reference Example II-1 II-G1, use separately Except for the color material dispersion liquids II-G2~II-G10 and II-CG1~II-CG4, the rest was carried out in the same manner as in (2) of Reference Example II-1 to obtain a photosensitive colored resin composition for color filters II- G2~II-G10, II-CG1~II-CG4.

(3) Formation of colored layer

In Reference Example II-1 (3), in addition to replacing the photosensitive colored resin composition II-G1, the above-mentioned photosensitive colored resin composition II-G2~II-G10, II-CG1~II-CG4 were used, respectively, The rest is the same as (3) of Reference Example II-1 to obtain colored layers II-G2 to II-G10 and II-CG1 to II-CG4.

(Examples II-7~II-10)

(1) Manufacturing of photosensitive colored resin composition II-G11~II-G14 for color filters

In Examples II-7 to II-10, in addition to replacing the color material dispersion liquid II-G1 in (2) of Reference Example II-1, the above color material dispersion liquid II-G2 was used, and the photoinitiator was changed Except for those described in Table 12, the rest was performed in the same manner as (2) of Reference Example II-1 to obtain photosensitive colored resin compositions II-G11 to II-G14 for color filters.

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，(股)BASF製，IRG907)0.10質量份及2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF製，IRG369)0.05質量份以外，其餘與參考例II-1之(2)同樣進行，得到彩色濾光片用感光性著色樹脂組成物II-G13。 In Example II-9, in addition to replacing the ethyl ketone in (2) of Reference Example II-1, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole- 3-yl]-,1-(o-acetyloxime) 0.02 parts by mass, changed to 2-methyl-1-(4-methylthiophenyl)-2-

Altopropan-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF, IRG907) 0.10 parts by mass and 2-benzyl-2-dimethylamino-1-(4-

Alrinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF, IRG369), except for 0.05 parts by mass, the rest was carried out in the same manner as in Reference Example II-1 (2) to obtain a color filter Photosensitive colored resin composition II-G13.

(3) Formation of colored layer

In (3) of Reference Example II-1, except that the photosensitive colored resin composition II-G1 was replaced with the above-mentioned photosensitive colored resin composition II-G11~II-G14, the rest was the same as that of Reference Example II-1 (3) The same procedure was performed to obtain colored layers II-G11 to II-G14.

(Reference Example II-5, Comparative Example II-C5)

In Reference Example II-5, in Reference Example II-1 (3), except that the film thickness is adjusted to form a colored layer in such a way that the chromaticity of y=0.50 under C light source, the rest is the same as Reference Example II-1 Step (3) is performed in the same way to form the colored layer II-G15.

In addition, in Comparative Example II-C5, in (3) of Reference Example II-1, in addition to replacing the photosensitive colored resin composition II-G1, the photosensitive colored resin composition II- obtained in Comparative Example II-C2 was used. For CG2, the coloring layer was formed by adjusting the film thickness so that the chromaticity of y=0.50 under the light source C, and the rest was performed in the same manner as (3) of Reference Example II-1 to form the coloring layer II-CG5.

[Table 12]

Here, the abbreviations in the table are as follows.

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

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

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

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

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

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

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

TR-PBG-304: oxime ester-based photoinitiator (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

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

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

[Evaluation method]

<Evaluation of Dispersibility of Color Material Dispersion>

For the color material dispersions obtained in the Reference Examples, Examples, and Comparative Examples, the viscosity immediately after preparation and after storage at 25°C for 30 days were measured, and the viscosity change rate was calculated from the viscosity before and after storage, and the viscosity stability was evaluated. In the viscosity measurement system, a vibrating viscometer was used to measure the viscosity at 25.0±0.5°C. The results are shown in Table 12.

(Evaluation criteria for dispersion stability)

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

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

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

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

However, it is a value when the color material is 13% by mass relative to the total mass of the solvent containing the color material dispersion liquid.

Although the color material dispersion liquid whose evaluation result is C can be used for practical use, if the evaluation result is B, the color material dispersion liquid is more favorable, 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, chromaticity (x, y), and brightness (Y) of the colored layers obtained in the Reference Examples, Examples, and Comparative Examples were measured using a contrast measuring device CT-1B manufactured by Kosaka Electric and a microscope OSP-SP200 manufactured by Olympus.

Furthermore, in Comparative Example 1 using PG58 as a pigment, the chromaticity of y=0.4 and x=0.2 under C light source could not be realized.

The results are shown in Table 12 together.

(Color reproduction gamut evaluation criteria)

‧Set the value when y=0.4~0.5 under C light source

A: x=0.21 is not full

B: x=0.21~0.23

C: x = more than 0.23

(Brightness evaluation standard)

‧Set the value when y=0.4 and x=0.2 under C light source

A: More than 50.0

B: 47.5~50.0

C: less than 47.5

‧Set the value when y=0.5 under C light source

A: Over 30.0

B: 30.0~25.0

C: less than 25.0

(Comparative evaluation criteria)

‧Set the value when y=0.4 and x=0.2 under C light source

A: More than 15000

B: 13500~15000

C: less than 13500

‧Set the value when y=0.5 under C light source

A: More than 3500

B: 2500~3500

C: less than 2500

<Evaluation of solvent resolubility>

The front end of a glass substrate with a width of 0.5 cm and a length of 10 cm was immersed in the reference example and the actual The photosensitive colored resin composition for color filters obtained in the Examples and Comparative Examples was coated on the 1 cm long portion of the glass substrate. The pulled up glass substrate is placed in a constant temperature and humidity machine so that the glass surface is horizontal, and it is dried under the conditions of a temperature of 23° C., a humidity of 80% RH and 10 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. The re-dissolution state of the dried coating film at this time was visually judged and evaluated. The results are shown in Table 12 together.

(Evaluation criteria for solvent resolubility)

A: The dried coating film is completely dissolved

B: Thin slices of dry coating film produced in the solvent, the solution is colored

C: No dry film is produced in the solvent, and the solution is not colored

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

<Evaluation of developing residue>

The photosensitive colored resin compositions for color filters obtained in the reference examples, examples and comparative examples were respectively applied to a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm and a thickness of 100 mm × 100 mm After coating using a spin coater, use a hot plate to dry at 60°C for 3 minutes to form a 2.5μm thick colored layer. The above-mentioned glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkali developer. After visually observing the unexposed part (50mm×50mm) of the glass substrate after the colored layer is formed, wipe it with a lens cleaning cloth containing ethanol (Toraysee MK cleaning cloth, trade name), and observe the lens visually The degree of coloration of the cleaning cloth. The results are shown in Table 12.

(Evaluation criteria for developing residue)

A: No development residue is visually confirmed, and the lens cleaning cloth is not colored at all.

B: No development residue was visually confirmed, but slight coloration of the lens cleaning cloth was confirmed.

C: A slight development residue is visually confirmed, and a slight coloration of the lens cleaning cloth is confirmed.

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

E: The development residue is visually confirmed, and the coloring of the lens cleaning cloth is 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 then A, the effect is more excellent.

<Evaluation of developing adhesion>

The photosensitive colored resin compositions for color filters obtained in the reference examples, examples and comparative examples were respectively applied to a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm and a thickness of 100 mm × 100 mm After coating using a spin coater, use a hot plate to dry at 60°C for 3 minutes to form a 2.5μm thick colored layer. For this colored layer, an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of ^{60 mJ/cm 2 through a mask having a mask opening width of 2 to 80 μm.} The above-mentioned glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkali developer. Observe the developed substrate with an optical microscope to observe whether there is a colored layer relative to the line width of the mask opening. The results are shown in Table 12.

(Evaluation Criteria for Developing Adhesiveness)

A: The colored layer is observed in the part where the line width of the mask opening is less than 10 μm.

B: The colored layer is observed in the part where the line width of the mask opening is 10 μm or more and less than 20 μm.

C: The colored layer is observed in the part where the line width of the mask opening is 20 μm or more and less than 50 μm.

D: A colored layer is observed in the part where the line width of the mask opening is 50 μm or more and less than 80 μm.

E: No colored layer is observed in the part where the line width of the mask opening is 80 μm or less.

If the above evaluation criteria are A, B, or C, it can be used for practical purposes; however, if the evaluation result is B or even A, the photosensitive colored resin composition for color filters is suitable for more refined applications.

<Evaluation of development tolerance>

The photosensitive colored resin compositions for color filters obtained in the Reference Examples, Examples and Comparative Examples were applied to a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm, and spin-coated. After coating the device, use a heating plate to heat and dry at 80°C for 3 minutes, and then use an ultra-high pressure mercury lamp to irradiate 40mJ/cm ² of ultraviolet rays. The film thickness at this point was measured, and it was taken as T1 (μm). After that, shower development was performed using a 0.05% by mass potassium hydroxide aqueous solution as an alkali developer. The film thickness after development was measured as T2 (μm). Calculate T2/T1×100(%). The results are shown in Table 12.

(Evaluation Criteria for Development Resistance)

A: More than 95%

B: More than 90% and less than 95%

C: Less than 90%

If the evaluation result is B, it can be used for practical use, but if the above-mentioned evaluation criterion is A, the effect is more excellent.

<Evaluation of Water Penetration>

The photosensitive colored resin composition for color filters obtained in each reference example, example and each comparative example was post-baked on a glass substrate (manufactured by NH TECHNO GLASS, "NA35") using a spin coater After baking, the coloring layer with a thickness of 1.6μm is formed. After coating, it is dried on a hot plate at 60°C for 3 minutes. ^{The ultraviolet light of 60mJ/cm 2} is irradiated on the glass by using an ultra-high pressure mercury lamp without masking. A colored layer is formed on the substrate. Next, use 0.05wt% potassium hydroxide (KOH) as a developer for rotational development, make it contact with the developer for 60 seconds, and then wash with pure water for development. The cleaned substrate is rotated for 10 seconds to centrifuge Immediately after removing the water, the contact angle of pure water was measured as follows to evaluate the water bleeding.

The contact angle of pure water is measured by dropping a drop of 1.0 μL of pure water on the surface of the colored layer just after the water has been removed by centrifugation, and measuring the static contact angle after 10 seconds by the θ/2 method. The measuring device was measured using a contact angle meter DM500 manufactured by Kyowa Interface Science Co., Ltd.

(Evaluation criteria)

A: The contact angle is above 80 degrees

B: The contact angle is more than 65 degrees but less than 80 degrees

C: The contact angle is more than 50 degrees but less than 65 degrees

D: The contact angle is less than 50 degrees

If the water bleeding evaluation criterion is A or B, it can be used for practical purposes; but if the evaluation result is A, the effect is even more excellent.

[Result integration]

From the results in Table 12, it is obvious that the C.I. Pigment Green 59 will be a general The color material dispersion liquids of Reference Examples II-1 to II-4 and Examples II-1 to II-6 of the polymer dispersant combination of the constituent unit represented by formula (I) have good viscosity stability. On the other hand, the color material dispersions of Comparative Examples II-C3 to II-C4 in which C.I. Pigment Green 59 was combined with a urethane-based dispersant or a polyester-based dispersant had significantly deteriorated viscosity stability. In addition, the color material dispersion liquid of Comparative Example II-C2 in which C.I. Pigment Green 7 was combined with a dispersant belonging to a polymer having a structural unit represented by the general formula (I), the viscosity stability was significantly deteriorated.

For the color filters of Reference Examples II-1~II-5 and Examples II-1~II-10 in which CI Pigment Green 59 is combined with a dispersant that is a polymer having a structural unit represented by the general formula (I) The photosensitive colored resin composition can display the area of x=0.20 when y=0.40, or it can display the area of x=0.16 with bluish green and high brightness when y=0.50. In addition, the color filters of Reference Examples II-1 to II-5 and Examples II-1 to II-10 in which CI Pigment Green 59 is combined with a dispersant that is a polymer having a structural unit represented by the general formula (I) The photosensitive colored resin composition for a sheet has good dispersion stability of the color material, excellent contrast, and excellent solvent resolubility, thereby suppressing the occurrence of development residue.

Wherein, as a dispersant, it is a block copolymer having an A block containing the structural unit represented by the above general formula (I) and a B block containing a structural unit derived from a carboxyl group-containing monomer and having a solvent affinity; or A salt-type block copolymer that forms a salt with at least a part of the nitrogen site of the constituent unit represented by the general formula (I); and the acid value of the dispersant is 1 mgKOH/g or more and 18 mgKOH/g or less, the dispersant In Examples II-1 to 3, 6, and 7 to 10 of the dispersant having a glass transition temperature of 30°C or higher, the occurrence of development residue was particularly suppressed, and the development adhesion was excellent.

On the other hand, as shown in Comparative Example II-C1, if C.I. Pigment Green 58 is used, when y=0.4, the area of x=0.2 cannot be displayed. Also, as shown in Comparative Example II-C2, if C.I. Pigment Green 7 is used, when y=0.4, the area of x=0.2 can be displayed, but The brightness is low. As shown in Comparative Example II-C5, if C.I. Pigment Green 7 is used, when y=0.50, although the area of x=0.16 can be displayed, the brightness is low. Also, although it is not shown in the table, with C.I. Pigment Green 58, when y=0.50, the area of x=0.16 cannot be displayed.

Also, as shown in Comparative Example II-C2, if CI Pigment Green 7 is used, even if it is combined with a dispersant that belongs to a polymer having a structural unit represented by the general formula (I), the dispersibility is still poor, so the contrast is low , Re-solubility and residue are also degraded.

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

In addition, in the examples, the examples in which the oxime ester-based photoinitiator is used as the photoinitiator, the development resistance and the effect of suppressing the occurrence of water bleeding are significantly increased.

Embodiment III series: the second embodiment of the present invention

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

(Reference example III-1)

(1) Manufacturing of color material dispersion III-G1

6.22 parts by mass of dispersant a solution as a dispersant, 5.33 parts by mass of CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) as a color material, and CI Pigment Yellow 138 (PY138, trade name: CHROMOFINE) YELLOW 6206EC, manufactured by Dainichi Chemical Industry Co., Ltd.) 7.67 parts by mass, alkali 14.59 parts by mass of soluble resin A solution, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0mm are placed in a beauty milk bottle, and shaken with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preparation Disintegrate, then take out the zirconia beads with a diameter of 2.0mm, add 200 parts by mass of the zirconia beads with a diameter of 0.1mm, and disperse for 4 hours with a pigment shaker as the formal disintegration to obtain a color material dispersion III-G1 .

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

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF(股)製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF製)0.04質量份、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名ADEKA ARKLS NCI-831，ADEKA公司製)0.02質量份、氟系界面活性劑(商品名MEGAFACE F559，DIC(股)製)0.07質量份、PGMEA7.14質量份，得到彩色濾光片用感光性著色樹脂組成物III-G1。 Add 11.40 parts by mass of color material dispersion III-G1 obtained in (1) above, 0.64 parts by mass of alkali-soluble resin A solution, and 0.60 mass of polyfunctional monomer (trade name ARONIX M-403, manufactured by Toagosei Co., Ltd.) Parts, 2-methyl-1-(4-methylthiophenyl)-2-

Hydroxypropane-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alkynylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) -9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (commodity MEGAFACE F559, manufactured by DIC Corporation) 0.07 parts by mass and 7.14 parts by mass of PGMEA, to obtain a photosensitive colored resin composition III-G1 for color filters.

(3) Formation of colored layer

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

(Reference Examples III-2~III-4, Examples III-1~III-6, Comparative Examples III-C1~III-C5)

(1) Manufacturing of color material dispersions III-G2~III-G10, III-CG1~III-CG5

In (1) of Reference Example III-1, except that as shown in Table 13, instead of dispersant a solution, the type and amount of dispersant used were changed to make the solid content the same parts by mass. Comparative Example III-C1 In ~III-C3, the color material was changed and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. The rest was performed in the same manner as in (1) of Reference Example III-1 to obtain color material dispersion liquids III-G2 to III-G10, III-CG1~III-CG5.

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

In Reference Examples III-2 to III-4, Examples III-1 to III-6, and Comparative Examples III-C1 to III-C5, except for replacing the color material dispersion in (2) of Reference Example III-1 Liquid III-G1, using the above-mentioned color material dispersion liquids III-G2~III-G10 and III-CG1~III-CG5, respectively, and adjust the amount of alkali-soluble resin to make the above-mentioned P/V ratio in order to make the film thickness to 2.35μm Except for the values shown in Table 13, the rest was performed in the same manner as (2) of Reference Example III-1 to obtain photosensitive colored resin compositions III-G2 to III-G10, III-CG1 to III-CG5 for color filters .

(3) Formation of colored layer

In Reference Example III-1 (3), except for replacing the photosensitive colored resin composition III-G1, the above-mentioned photosensitive colored resin composition III-G2~III-G10, III-CG1~III-CG5 were used respectively , And the rest is the same as (3) of Reference Example III-1 to obtain colored layers III-G2 to III-G10 and III-CG1 to III-CG5.

(Example III-7~III-10, III-29)

(1) Manufacturing of photosensitive colored resin composition III-G11~III-G14, III-33 for color filters

In Examples III-7 to III-8 and III-29, in order to replace the color material dispersion liquid III-G1 in (2) of Reference Example III-1, the above color material dispersion liquid III-G2 was used, and further The photoinitiator was changed to those described in Table 13, and the rest was carried out in the same manner as in (2) of Reference Example III-1 to obtain photosensitive colored resin compositions for color filters III-G11 to III-G12, III-G33 .

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF(股)製)0.10質量份及2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF製)0.05質量份以外，其餘與參考例III-1之(2)同樣進行，得到彩色濾光片用感光性著色樹脂組成物III-G13。 In addition, in Example III-9, in order to replace the color material dispersion liquid III-G1 in (2) of Reference Example III-1, the above color material dispersion liquid III-G2 was used instead of the color material dispersion liquid III-G2 of Reference Example III-1. (2) Ethyl ketone, 1-(9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-,1-(o-acetyloxime)0.02 Parts by mass, changed to 2-methyl-1-(4-methylthiophenyl)-2-

Altopropane-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF Co., Ltd.) 0.10 parts by mass and 2-benzyl-2-dimethylamino-1-(4-

Alolinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF), except for 0.05 parts by mass, the rest was carried out in the same manner as in Reference Example III-1 (2) to obtain a photosensitive color filter Colored resin composition III-G13.

In addition, in Example III-10, the color material dispersion liquid III-G2 was used instead of the color material dispersion liquid III-G1 of (2) of Reference Example 1, and further replaced the alkali soluble resin A solution as an alkali soluble resin , Changed to alkali-soluble resin B solution (epoxy (meth)acrylate resin with carboxyl group containing carbodole structure, model INR-16M, manufactured by Nagase ChemteX (stock)), and became the same mass part according to the solid content Except for the method of adjusting the usage amount, the rest was performed in the same manner as (2) of Reference Example III-1 to obtain the photosensitive colored resin composition III-G14 for color filters.

(3) Formation of colored layer

In (3) of Reference Example III-1, except for replacing the photosensitive colored resin composition III-G1, the above-mentioned photosensitive colored resin composition III-G11~III-G14 and III-G33 were used, respectively, and the rest is the same as the reference Example III-1 (3) was carried out in the same way to obtain colored layers III-G11 to III-G14 and III-G33.

[Table 13]

Here, the abbreviations in the table are as follows.

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

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

In addition, the G58, G7, byk-2000, N21116, byk-161, PB822, NCI-831, TR-PBG-304, OXE03, and NCI-930 series are the same as the Example II series.

(Examples III-11 to III-16, Comparative Example III-C6)

(1) Manufacturing of color material dispersion III-G15~III-G20, III-CG8

In (1) of Reference Example III-1, in addition to changing the color material type and usage amount as shown in Table 14, the type and usage amount of the dispersant were changed so that the solid content becomes the same part by mass, and the total is Except for adjusting the amount of PGMEA to 100 parts by mass, the same procedure was performed as in (1) of Reference Example III-1 to obtain color material dispersion liquids III-G15 to III-G20 and III-CG8.

(2) Manufacturing of photosensitive colored resin composition III-G15~III-G20, III-CG8 for color filters

Except for replacing the color material dispersion liquid III-G1 in (2) of Reference Example III-1, the above color material dispersion liquids III-G15~III-G20 and III-CG8 were used respectively, and in order to make the film thickness 2.80μm Therefore, the amount of alkali-soluble resin was adjusted so that the above-mentioned P/V ratio became the values shown in Table 14, and the rest was performed in the same manner as (2) of Reference Example III-1 to obtain photosensitive colored resin composition III for color filters -G15~III-G20, III-CG8.

(3) Formation of colored layer

In Reference Example III-1 (3), except for replacing the photosensitive colored resin composition III-G1, except that the above-mentioned photosensitive colored resin composition III-G15~III-G20 and III-CG8 were used, and the rest was carried out in the same manner as (3) of Reference Example III-1 to obtain colored layers III-G15~III-G20 , III-CG8. In addition, in Comparative Example III-C6 using PG58 as the color material, the chromaticity of y=0.610 and x=0.210 under C light source could not be achieved.

[Table 14]

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: Derivative pigment of C.I. Pigment Yellow 150 prepared by the following preparation example (azo pigment with Ni:Zn=1:1 (molar ratio))

(Modulation example)

After 550g of distilled water, 23.1g of diazobarbituric acid and 19.2g of barbituric acid were introduced. Next, it was adjusted to azobarbituric acid (0.3 mol) using a potassium hydroxide aqueous solution, and mixed with 750 g of distilled water. Add 5g of 30% hydrochloric acid by dropping. After that, 38.7 g of melamine was introduced. Next, 0.3 mol of nickel chloride solution and 0.3 mol of zinc chloride solution were mixed and added, and stirred at 80°C for 8 hours. The pigment is separated by filtration, washed, dried at 120°C, and ground with a mortar to obtain the derivative pigment of C.I. Pigment Yellow 150.

(Examples III-17 to III-21, Comparative Example III-C7)

(1) Manufacturing of color material dispersion III-G21~III-G25, III-CG9

In (1) of Reference Example III-1, in addition to changing the type and amount of color material as shown in Table 15, then the type and amount of dispersant were changed so that the solid content becomes the same part by mass, and the total Except for adjusting the amount of PGMEA so as to be 100 parts by mass, the same procedure was performed as in (1) of Reference Example III-1 to obtain color material dispersion liquids III-G21 to III-G25 and III-CG9.

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

Except for replacing the color material dispersion liquid III-G1 in (2) of Reference Example III-1, use Use the above-mentioned color material dispersion liquids III-G21~III-G25 and III-CG9, and adjust the amount of alkali-soluble resin in order to make the film thickness 2.80μm so that the above-mentioned P/V ratio becomes the value shown in Table 15, and the rest In the same manner as (2) of Reference Example III-1, photosensitive colored resin compositions III-G21 to III-G25 and III-CG9 for color filters were obtained.

(3) Formation of colored layer

In Reference Example III-1 (3), except that the photosensitive colored resin composition III-G1 was replaced with the above-mentioned photosensitive colored resin composition III-G21~III-G25, and III-CG9, the rest is the same as the reference example III-1 (3) was performed in the same way to obtain colored layers III-G21 to III-G25 and III-CG9. In addition, in Comparative Example III-C7 using PG58 as the color material, the chromaticity of y=0.626 and x=0.205 under the C light source could not be achieved.

[Table 15]

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 Co., Ltd.)

(Example III-22~III-24)

(1) Manufacturing of color material dispersion III-G26~III-G28

In (1) of Reference Example III-1, in addition to changing the type and amount of color material as shown in Table 16, the type and amount of dispersant were changed so that the solid content becomes the same part by mass, and the total Except that the amount of PGMEA was adjusted so as to be 100 parts by mass, the same procedure was performed as in (1) of Reference Example III-1 to obtain color material dispersion liquids III-G26 to III-G28.

(2) Manufacturing of photosensitive colored resin composition III-G26 to III-G28 for color filters

Except for replacing the color material dispersion liquid III-G1 in (2) of Reference Example III-1, the above color material dispersion liquids III-G26~III-G28 were used respectively, and the alkali-soluble resin was adjusted in order to make the film thickness to 3.30μm Except that the above-mentioned P/V ratio becomes the value shown in Table 16, the rest is performed in the same manner as (2) of Reference Example III-1 to obtain photosensitive colored resin composition for color filters III-G26~III- G28.

(3) Formation of colored layer

In (3) of Reference Example III-1, except for replacing the photosensitive colored resin composition III-G1, and using the above-mentioned photosensitive colored resin composition III-G26~III-G28 respectively, the rest is the same as that of Reference Example III-1 Step (3) is performed in the same way to obtain colored layers III-G26 to III-G28.

[Table 16]

(Example III-25~III-27)

(1) Manufacturing of color material dispersion III-G29~III-G31

In (1) of Reference Example III-1, in addition to changing the type and amount of color material as shown in Table 17, the type and amount of dispersant are changed so that the solid content becomes the same part by mass, and the total Except for adjusting the amount of PGMEA so as to be 100 parts by mass, the same procedure was performed as in (1) of Reference Example III-1 to obtain color material dispersion liquids III-G29 to III-G31.

(2) Manufacturing of photosensitive colored resin composition III-G29 to III-G31 for color filters

Except for replacing the color material dispersion liquid III-G1 in (2) of Reference Example III-1, use The color material dispersion liquids III-G29 to III-G31 were used, and in order to make the film thickness 3.30μm, the amount of alkali-soluble resin was adjusted so that the above-mentioned P/V ratios were other than those shown in Table 17, and the rest was the same as Reference Example III -1 (2) was carried out in the same manner to obtain photosensitive colored resin compositions III-G29 to III-G31 for color filters.

(3) Formation of colored layer

In (3) of Reference Example III-1, except that the photosensitive colored resin composition III-G1 was substituted for the photosensitive colored resin composition III-G1, the above-mentioned photosensitive colored resin composition III-G29 to III-G31 were used, and the rest was the same as that of Reference Example III-1 Step (3) is performed in the same way to obtain colored layers III-G29 to III-G31.

[Table 17]

(Example III-28)

(1) Manufacturing of color material dispersion

Dispersant b solution 6.22 parts by mass as a dispersant, CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC (stock) system) 13 parts by mass as a color material, 14.59 parts by mass of alkali-soluble resin A solution, PGMEA66. 20 parts by mass and 100 parts by mass of zirconia beads with a particle size of 2.0mm are placed in the beauty milk bottle, shaken with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preparatory disintegration, and then take out the oxidation with a particle size of 2.0mm To the zirconium beads, 200 parts by mass of zirconium oxide beads with a particle diameter of 0.1 mm were added, and the dispersion was carried out in the same manner for 4 hours with a pigment shaker as a formal disintegration to obtain a green color material dispersion liquid g.

6.22 parts by mass of dispersant b solution as a dispersant, 13 parts by mass of CI Pigment Yellow 138 (PY138, trade name: CHROMOFINE YELLOW 6206EC, manufactured by Dainichi Seiki Chemical Co., Ltd.) as a color material, and 14.59 parts of alkali-soluble resin A solution Parts by mass, 66.20 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0mm are placed in a beauty milk bottle, shaken with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preparatory disintegration, and then taken out Zirconia beads with a particle size of 2.0 mm were added to 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and dispersion was performed for 4 hours with a pigment shaker as a formal disintegration to obtain a yellow color material dispersion liquid y.

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

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF(股)製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF 製)0.04質量份、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名ADEKA ARKLS NCI-831，ADEKA公司製)0.02質量份、氟系界面活性劑(商品名MEGAFACE F559，DIC(股)製)0.07質量份、PGMEA7.14質量份，得到彩色濾光片用感光性著色樹脂組成物III-G32。 Add 4.67 parts by mass of the green color material dispersion g obtained in (1) above, 6.73 parts by mass of the yellow color material dispersion y, 0.64 parts by mass of alkali-soluble resin A solution, and polyfunctional monomer (trade name ARONIX M-403, East Asia) Synthetic Co., Ltd.) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl)-2-

Hydroxypropane-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alolinylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) -9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (commodity Name MEGAFACE F559, manufactured by DIC Corporation) 0.07 parts by mass and 7.14 parts by mass of PGMEA, to obtain a photosensitive colored resin composition III-G32 for color filters.

(3) Formation of colored layer

In Reference Example III-1 (3), except that the photosensitive colored resin composition III-G32 was used instead of the photosensitive colored resin composition III-G1, the rest was the same as Reference Example III-1 (3) Proceed to obtain the colored layer III-G32.

The obtained photosensitive colored resin composition III-G32 for color filters has the same composition as the photosensitive colored resin composition III-G2 for color filters of Example III-1, and the photosensitive colored resin composition for color filters The evaluation results of the composition III-G32 and the colored layer III-G32 are the same as the evaluation results of the photosensitive colored resin composition III-G2 and the colored layer III-G2 for color filters.

[Evaluation Method of Example III Series]

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

<Optical performance evaluation, comparative evaluation>

Using the comparison measuring device CT-1B made by Kosaka Electric and the OSP-SP200 made by Olympus microscope to measure the coloring layer of the reference examples, examples and comparative examples Contrast and chromaticity (x, y), brightness (Y).

Moreover, in Comparative Example 6 using PG58 as the color material, the chromaticity of y=0.610 and x=0.210 under C light source could not be achieved. In Comparative Example 7 using PG58 as the color material, the chromaticity of y=0.626 and x=0.205 under C light source could not be achieved.

(Comparative evaluation criteria) ‧Set the value when y=0.570 and x=0.260 under C light source

A: More than 12000

B: 12000~10000

C: less than 10000

<Display Bad Evaluation>

Using the dielectric impedance measurement system 126096W (manufactured by Toyo Technical), the display failure evaluation of the colored layers obtained in the reference examples, the examples, and the comparative examples was performed.

(Display bad evaluation criteria)

A: The loss factor (tanδ) under 100Hz is less than 0.023

B: The loss factor (tanδ) at 100Hz is 0.023~0.048

C: The loss factor (tanδ) under 100Hz exceeds 0.048

If the above-mentioned evaluation criterion is A or B, it can be used for practical purposes, and if the evaluation result is A, it shows that the defect suppression effect is high.

[Example III System Results Integration]

From the results in Tables 13-17, it is obvious that the color material dispersion liquid of the embodiment in which PG59 and the yellow color material are combined with the dispersant of the polymer having the constituent unit represented by the general formula (I) has stable viscosity Good sex. On the other hand, PG59 is combined with carbamate The color material dispersion liquids of Comparative Examples III-C4 to III-C5 of the ethyl acid-based dispersant or the polyester-based dispersant have markedly deteriorated viscosity stability. In addition, the color material dispersions of Comparative Examples III-C1, III-C2, and III-C3 in which a dispersant belonging to a polymer having a structural unit represented by the general formula (I) is combined in PG58 or PG7 or PG36, and its viscosity The stability is obviously inferior to that of Reference Example III-1 in which the same dispersant is combined. In addition, the dispersion material liquids of Comparative Examples III-C2 and III-C3 in which a dispersant belonging to a polymer having a structural unit represented by the general formula (I) was combined in PG7 or PG36, the dispersibility was deteriorated.

It is obvious from Table 13 that reference examples III-1 to III-4 and Example III-1 were combined with a yellow color material in PG59 and a dispersant which is a polymer having a structural unit represented by the general formula (I). The photosensitive colored resin composition for color filters of ~III-10, when y=0.570, can display the area of x=0.260, and suppress the occurrence of display defects, and can form a high-brightness colored layer. In addition, it is obvious that PG59 is a combination of the yellow color material PY138, and the reference examples III-1 to III-4 and the examples III-1 to the combination of the dispersant belonging to the polymer having the structural unit represented by the general formula (I). The photosensitive colored resin composition for color filters of III-10 clearly shows that the color material dispersion stability is good, the contrast is excellent, the solvent resolubility is excellent, and the occurrence of development residue is suppressed.

Among them, as a dispersant, a block copolymer having an A block containing the structural unit represented by the above general formula (I) and a solvophilic B block containing a structural unit derived from a carboxyl group-containing monomer is used; or The salt type block copolymer in which at least a part of the nitrogen site 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. In Examples III-1~III-2, III-6, III-7~III-10, and III-29 of the dispersant with a glass transition temperature of 30°C or higher, the occurrence of development residues was particularly suppressed, and the development of dense adhesion Excellent. In addition, an epoxy (meth)acrylate resin with a carboxyl group containing a carbodole structure is used as the photosensitive coloring Example III-10 of the alkali-soluble resin in the resin composition is superior to Example III-1 in terms of development adhesion, development resistance, and water bleeding suppression effect.

Moreover, in the examples, from the comparison of Examples III-1, III-7, III-8, III-9 and III-29, it is obvious that the implementation of using oxime ester-based photoinitiators as photoinitiators For example, the development resistance and the effect of inhibiting the occurrence of water bleeding become higher.

In addition, it is obvious from Table 14 and Table 15 that if a yellow color material is combined with PG59, a dispersant belonging to a polymer having a structural unit represented by the general formula (I), the color reproduction gamut will increase, at y=0.570~ In the case of 0.626, the chromaticity region of x=0.205~0.324 can still be displayed, and the chromaticity region of y=0.659 can be displayed. The occurrence of poor display can be obviously suppressed, and a high-brightness colored layer can be formed.

In addition, in Example III-23 of Table 16, if PG58 is further combined with PG59 and yellow color material, compared with Example III-22 where PG59 is used alone as the green color material, the above P/V ratio is obviously Reduced, and the brightness is more improved. In Example III-24, if PG59 and PG58, which are green color materials, and PY138 and PY150, which are yellow color materials, are combined, the above-mentioned P/V ratio is significantly reduced.

In addition, in Examples III-26 of Table 17, if PG7 is further combined with PG59 and yellow color material, the above-mentioned P/V ratio is obviously reduced, and the brightness is also improved. In Example III-27, if PG59 and PG7, which are green color materials, and PY138 and PY150, which are yellow color materials, are combined, the above-mentioned P/V ratio is significantly reduced.

On the other hand, as shown in Comparative Example III-C1, if PG58 is used, when y=0.570, although the area of x=0.260 can be displayed, poor display occurs, and its brightness is worse than when PG59 is used. In addition, the development residue also deteriorated. Also, as shown in Comparative Examples III-C2 and III-C3, if PG7 or PG36 is used, when y=0.570, although the area of x=0.260 can be displayed, the brightness is low. Moreover, even if it will belong to the constituent unit represented by the general formula (I) When polymer dispersants are used in combination, the dispersibility is still deteriorated, so the contrast is low, and the resolubility and residue are also deteriorated.

On the other hand, the photosensitive colored resin composition for color filters of Comparative Examples III-C4 to III-C5 in which PG59 is combined with a urethane-based dispersant or a polyester-based dispersant is dispersed The performance is deteriorated, so compared with the embodiment, the brightness is reduced, and the contrast is low, and the resolubility and residue are also deteriorated.

Example IV Series: The second third embodiment of the present invention

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

(Reference Example IV-1)

(1) Manufacturing of color material dispersion IV-G1

6.22 parts by mass of dispersant a solution as a dispersant, 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 Dainichi Seiki Chemical Co., Ltd.) 1.39 parts by mass, as a yellow color material, CI Pigment Yellow 139 (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, 14.59 parts by mass of alkali-soluble resin A solution, 66.20 parts by mass of PGMEA, zirconia beads with a particle size of 2.0 mm 100 parts by mass of the ball is placed in a beauty milk bottle, shaken with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preparatory disintegration, and then the particle size is taken out 2.0 mm zirconia beads, 200 parts by mass of zirconia beads with a particle size of 0.1 mm were added, and dispersed in a pigment shaker for 4 hours as a formal disintegration to obtain a color material dispersion IV-G1.

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

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF(股)製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF製)0.04質量份、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名ADEKA ARKLS NCI-831，ADEKA公司製)0.02質量份、氟系界面活性劑(商品名MEGAFACE F559，DIC(股)製)0.07質量份、PGMEA9.72質量份，得到彩色濾光片用感光性著色樹脂組成物IV-G1。 Add 11.41 parts by mass of color material dispersion IV-G1 obtained in (1) above, 2.75 parts by mass of alkali-soluble resin A solution, and 0.60 mass of polyfunctional monomer (trade name ARONIX M-403, manufactured by Toagosei Co., Ltd.) Parts, 2-methyl-1-(4-methylthiophenyl)-2-

Hydroxypropane-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alkynylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) -9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (commodity Name MEGAFACE F559, manufactured by DIC Corporation) 0.07 parts by mass and PGMEA 9.72 parts by mass, to obtain photosensitive colored resin composition IV-G1 for color filters.

(3) Formation of colored layer

The photosensitive colored resin composition IV-G1 obtained in (2) above was applied to a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") with a thickness of 0.7 mm and a thickness of 100 mm × 100 mm using a spin coater. After coating, use a hot plate to dry at 80°C for 3 minutes, use an ultra-high pressure mercury lamp to irradiate 60mJ/cm ² of ultraviolet rays, and then post-bake in a dust-free oven at 230°C for 30 minutes. The cured film thickness becomes 2.80μm. The film thickness is adjusted in the manner to form the colored layer IV-G1.

(Reference Examples IV-2~IV-4, Examples IV-1~IV-6, IV-11~IV-13, Comparative Examples IV-C1~IV-C4)

(1) Manufacturing of color material dispersions IV-G2~IV-G10, IV-G15~IV-G17, IV-CG1~IV-CG4

In Reference Examples IV-2 to IV-4, Examples IV-1 to IV-6, and Comparative Examples IV-C3 to IV-C4, in (1) of Reference Example IV-1, except as shown in Table 18 respectively In general, in order to replace the dispersant a solution, the type and amount of dispersant used are changed so that the solid content becomes the same part by mass, and the amount of PGMEA is adjusted so that the total is 100 parts by mass, and the rest are the same as those in Reference Example IV-1 ( 1) In the same manner, color material dispersion liquids IV-G2 to IV-G10 and IV-CG3 to IV-CG4 are obtained. In Examples IV-11 to IV-13, in (1) of Reference Example IV-1, in addition to replacing the dispersant a solution, the dispersant b solution was used, and the color materials were changed to 100 parts by mass in total Except that the amount of PGMEA was adjusted by the method, the same procedure was performed as in (1) of Reference Example IV-1 to obtain color material dispersion liquids IV-G15 to IV-G17. In Comparative Examples IV-C1 to IV-C2, in Reference Example IV-1 (1), except that the color material was changed, the rest was performed in the same manner as Reference Example IV-1 (1) to obtain IV-CG1~IV -CG2.

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

Except for replacing the color material dispersion IV-G1 in (2) of Reference Example IV-1, use the above color material dispersions IV-G2~IV-G10, IV-G15~IV-G17, IV-CG1~IV, respectively -CG4, in order to make the film thickness 2.8μm, adjust the amount of alkali-soluble resin so that the above P/V ratio becomes the value shown in Table 18, and the rest is performed in the same manner as (2) of Reference Example IV-1 to obtain Photosensitive colored resin composition IV-G2~IV-G10, IV-G15~IV-G17, IV-CG1~IV-CG4 for color filters.

(3) Formation of colored layer

In Reference Example IV-1 (3), in addition to replacing the photosensitive colored resin composition IV-G1, the above-mentioned photosensitive colored resin composition IV-G2~IV-G10, IV-G15~IV-G17, Except IV-CG1~IV-CG4, the rest was performed in the same manner as (3) of Reference Example IV-1 to obtain colored layers IV-G2~IV-G10, IV-G15~IV-G17, and IV-CG1~IV-CG4.

(Examples IV-7~IV-10, IV-32)

(1) Production of photosensitive colored resin composition IV-G11~IV-G14, IV-G36 for color filters

In Examples IV-7 to IV-8 and IV-32, in addition to replacing the color material dispersion IV-G1 in (2) of Reference Example IV-1, the above color material dispersion IV-G2 was used, and the The photoinitiator was changed to those described in Table 18, and the rest was carried out in the same manner as in (2) of Reference Example IV-1 to obtain photosensitive colored resin compositions IV-G11 to IV-G12, IV-G36 for color filters .

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF(股)製)0.10質量份及2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF製)0.05質量份以外，其餘與參考例IV-1之(2)同樣進行，得到彩色濾光片用感光性著色樹脂組成物IV-G13。 In addition, in Example IV-9, in addition to replacing the color material dispersion liquid IV-G1 in (2) of Reference Example IV-1, the above color material dispersion liquid IV-G2 was used instead of Reference Example IV-1 ( 2) Ethyl ketone in 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime)0.02 mass Parts, changed to 2-methyl-1-(4-methylthiophenyl)-2-

Altopropane-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF Co., Ltd.) 0.10 parts by mass and 2-benzyl-2-dimethylamino-1-(4-

Alolinophenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF), except for 0.05 parts by mass, the rest was carried out in the same manner as (2) of Reference Example IV-1 to obtain a photosensitive color filter Colored resin composition IV-G13.

In addition, in Example IV-10, in addition to replacing the color material dispersion IV-G1 of (2) of Reference Example IV-1, the above color material dispersion IV-G2 was used instead of the alkali-soluble resin. The alkali-soluble resin A solution of the fat is changed to the alkali-soluble resin B solution (epoxy (meth)acrylate resin with carboxyl group containing a carbodole structure, model INR-16M, manufactured by Nagase ChemteX (stock)). Except for adjusting the usage amount so that the solid content becomes the same part by mass, the same procedure was performed as in (2) of Reference Example IV-1 to obtain a photosensitive colored resin composition IV-G14 for color filters.

(3) Formation of colored layer

In Reference Example IV-1 (3), except that the photosensitive colored resin composition IV-G1 was replaced with the above-mentioned photosensitive colored resin composition IV-G11 to IV-G14 and IV-G36, the rest is the same as the reference example IV-1 (3) was performed in the same way to obtain colored layers IV-G11 to IV-G14 and IV-G36.

[Table 18]

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 Dainichi Chemical Industry Co., Ltd.)

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

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

(Examples IV-14~IV-15, Comparative Examples IV-C5~IV-C10)

(1) Manufacturing of color material dispersions IV-G18~IV-G19, IV-CG5, IV-CG 7~IV-CG11

In (1) of Reference Example IV-1, in addition to changing the color material type and usage amount as shown in Table 19, the type and usage amount of the dispersant are changed to the same mass parts as the solid content, and the total is 100 Except for adjusting the amount of PGMEA in parts by mass, the same procedure was performed as in (1) of Reference Example IV-1 to obtain color material dispersions IV-G18 to IV-G19, IV-CG5, and IV-CG 7 to IV-CG11.

(2) Manufacturing of photosensitive colored resin composition IV-G18~IV-G19, IV-CG5, IV-CG 7~IV-CG11 for color filters

Except for replacing the color material dispersion IV-G1 in (2) of Reference Example IV-1, the above color material dispersions IV-G18~IV-G19 and IV-CG7 were used, respectively, and in order to make the film thickness 2.8μm. The amount of alkali-soluble resin was adjusted so that the above P/V ratio became the values shown in Table 19, and the rest was performed in the same manner as (2) of Reference Example IV-1 to obtain a photosensitive colored resin composition IV- for color filters G18~IV-G19 and IV-CG7.

In the color material combination of Comparative Example IV-C5 and Comparative Examples IV-C7 to IV-C10, it was not possible to prepare a photosensitive colored resin composition with a film thickness of 2.8 μm and a chromaticity of x=0.200 and y=0.710.

(3) Formation of colored layer

In (3) of Reference Example IV-1, except for replacing the photosensitive colored resin composition IV-G1, the above-mentioned photosensitive colored resin composition IV-G18~IV-G19 and IV-CG7 were used respectively, and the rest is the same as the reference Example IV-1 (3) was performed in the same way to obtain colored layers IV-G18 to IV-G19 and IV-CG7.

[Table 19]

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

(Examples IV-16~IV-30)

(1) Manufacturing of color material dispersion IV-G20~IV-G34

In (1) of Reference Example IV-1, in addition to as shown in Table 20, the type and amount of color material are changed, and the type and amount of dispersant are changed so that the solid content becomes the same part by mass, so that the total Except for adjusting the amount of PGMEA so as to be 100 parts by mass, the same procedure was performed as in (1) of Reference Example IV-1 to obtain color material dispersion liquids IV-G20 to IV-G34.

(2) Manufacturing of photosensitive colored resin composition IV-G20~IV-G34 for color filters

Except for replacing the color material dispersion IV-G1 in (2) of Reference Example IV-1, the above color material dispersions IV-G20~IV-G34 were used respectively, and the alkali-soluble resin was adjusted in order to make the film thickness 2.8μm Except that the above-mentioned P/V ratio becomes the value shown in Table 20, the rest is carried out in the same manner as (2) of Reference Example IV-1 to obtain photosensitive colored resin composition for color filter IV-G20~IV- G34.

(3) Formation of colored layer

In Reference Example IV-1 (3), except that the photosensitive colored resin composition IV-G1 was substituted for the photosensitive colored resin composition IV-G1, the above-mentioned photosensitive colored resin composition IV-G20 to IV-G34 was used, and the rest was the same as that of Reference Example IV-1 Step (3) is performed in the same way to obtain colored layers IV-G20 to IV-G34.

[Table 20]

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

(Example IV-31)

(1) Manufacturing of color material dispersion

Dispersant b solution 6.22 parts by mass as a dispersant, CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC (stock) system) 13 parts by mass as a color material, 14.59 parts by mass of alkali-soluble resin A solution, PGMEA66. 20 parts by mass and 100 parts by mass of zirconia beads with a particle size of 2.0mm are placed in the beauty milk bottle, shaken with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preparatory disintegration, and then take out the oxidation with a particle size of 2.0mm To the zirconium beads, 200 parts by mass of zirconium oxide beads with a particle diameter of 0.1 mm were added, and the dispersion was carried out in the same manner for 4 hours with a pigment shaker as a formal disintegration to obtain a green color material dispersion liquid g.

In the above-mentioned green color material dispersion liquid g, instead of 13 parts by mass of CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Co., Ltd.) as the color material, CI Pigment Blue 15:4 (PB15:4) was used. Trade name: CYANINE BLUE CP-1, manufactured by Dainichi Seiki Chemical Co., Ltd.) 13 parts by mass as the color material, in the same manner as the above-mentioned green color material dispersion liquid g, to obtain a blue color material dispersion liquid b.

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

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

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

啉基丙烷-1-酮(光起始劑：商品名IRGACURE907，BASF(股)製)0.09質量份、2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁酮-1(光起始劑：商品名IRGACURE369，BASF製)0.04質量份、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)(光起始劑：商品名ADEKA ARKLS NCI-831，ADEKA公司製)0.02質量份、氟系界面活性劑(商品名MEGAFACE F559，DIC(股)製)0.07質量份、PGMEA9.72質量份，得到彩色濾光片用感光性著色樹脂組成物IV-G35。 Adding 5.63 parts by mass of the green material dispersion g obtained in (1) above, 1.22 parts by mass of the blue color material dispersion b, 1.23 parts by mass of the yellow color material dispersion y1, 3.33 parts by mass of the yellow color material dispersion y2, and synthesis example 9 Alkali-soluble resin A solution 2.75 parts by mass, polyfunctional monomer (trade name ARONIX M-403, manufactured by Toagosei Co., Ltd.) 0.60 parts by mass, 2-methyl-1-(4-methylthiophenyl) )-2-

Hydroxypropane-1-one (photoinitiator: trade name IRGACURE907, manufactured by BASF Co., Ltd.) 0.09 parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Alkynylphenyl)-butanone-1 (photoinitiator: trade name IRGACURE369, manufactured by BASF) 0.04 parts by mass, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) -9H-carbazol-3-yl]-,1-(o-acetyloxime) (photoinitiator: trade name ADEKA ARKLS NCI-831, manufactured by ADEKA) 0.02 parts by mass, fluorine-based surfactant (commodity Name MEGAFACE F559, manufactured by DIC Corporation) 0.07 parts by mass and PGMEA 9.72 parts by mass, to obtain photosensitive colored resin composition IV-G35 for color filters.

(3) Formation of colored layer

In reference example IV-1 (3), except that the photosensitive color resin composition IV-G35 is used in place of the photosensitive color resin composition IV-G1, the rest is the same as the reference example IV-1 (3) Proceed to obtain a colored layer IV-G35.

The obtained photosensitive colored resin composition IV-G35 for color filters has the same composition as the photosensitive colored resin composition IV-G2 for color filters of Example IV-1, and the photosensitive colored resin composition for color filters The evaluation results of composition IV-G35 and coloring layer IV-G35 are related to photosensitive coloring resin composition IV-G2 and coloring layer for color filters The evaluation results of IV-G2 are the same.

[Evaluation Method of Example IV Series]

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

<Optical performance evaluation, comparative evaluation>

The contrast and chromaticity (x, y) and brightness (Y) of the colored layers obtained in the reference examples, examples and comparative examples were measured using the comparison measuring device CT-1B made by Kosaka Electric and the OSP-SP200 microscopic light measuring device made by Olympus .

(Comparative evaluation criteria)

‧Set the value when y=0.670, x=0.210 under C light source

A: More than 8000

B: 6000~8000

C: less than 6000

[Example IV System Results Integration]

From the results in Tables 18-20, it is obvious that the color materials of the embodiment combining the dispersant of the polymer having the structural unit represented by the general formula (I) among the PG59 and the blue color material and the above-mentioned specific yellow color material The dispersion liquid has obviously good viscosity stability. On the other hand, the color material dispersions of Comparative Examples IV-C3 to IV-C4 in which PG59 was combined with a urethane-based dispersant or a polyester-based dispersant had significantly deteriorated viscosity stability. Also, at PG58 Or in PG36, the color material dispersions of Comparative Examples IV-C1 and IV-C2, which combine the dispersants of the polymer having the structural unit represented by the general formula (I), have significantly higher viscosity stability than those combined with the same dispersant Reference example IV-1 is poor. In addition, the color material dispersion liquid of Comparative Example IV-C2 in which a dispersant belonging to a polymer having a structural unit represented by the general formula (I) was combined in PG36, the dispersibility was deteriorated.

It is obvious from Table 18 that in PG59, the blue color material, the above-mentioned specific yellow color material, and the reference examples IV-1 to IV-4 of the dispersant combined with the polymer having the structural unit represented by the general formula (I) are implemented. Examples IV-1 to IV-13 and IV-32 of the photosensitive colored resin composition for color filters, when y=0.670, the area of x=0.210 can be displayed, and the occurrence of display failure can be suppressed, and the formation of high The color layer of brightness. In addition, it is obvious that the photosensitive colored resin composition for color filters of Reference Examples IV-1 to IV-4, Examples IV-1 to IV-13, and IV-32 have good color material dispersion stability. The contrast is excellent, and the solvent re-solubility is excellent, thereby suppressing the occurrence of development residue.

Among them, as a dispersant, a block copolymer having an A block containing the structural unit represented by the above general formula (I) and a solvophilic B block containing a structural unit derived from a carboxyl group-containing monomer is used; or The salt type block copolymer in which at least a part of the nitrogen site 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. A dispersant with a glass transition temperature of 30°C or higher, in particular, inhibits the occurrence of development residues, and has superior development adhesion (Example IV-1~IV-13 with the same P/V ratio and Example IV- in IV-32) 1. IV-2, IV-6, IV-7~IV-13 and IV-32). In addition, Example IV-10 using a carbodole-containing epoxy (meth)acrylate resin having a carboxyl group as the alkali-soluble resin in the photosensitive colored resin composition is compared to Example IV-1 in developing It is superior in adhesion, development resistance, and water bleeding prevention effect.

In addition, in the examples, from the comparison of Examples IV-1, IV-7, IV-8, IV-9 and IV-32, it is obvious that the implementation of using the oxime ester-based photoinitiator as the photoinitiator In the example, the development resistance and the effect of inhibiting the occurrence of water bleeding are significantly higher.

In addition, it is clear from Table 19 and Table 20 that if the blue color material and the above-mentioned specific yellow color material are combined with PG59 as a dispersant that belongs to a polymer having a structural unit represented by the general formula (I), the color reproduction gamut will be increased. In the case of y=0.570~0.720, the chromaticity region of x=0.140~0.265 can still be displayed, and the chromaticity region of y=0.750 can be displayed, which can obviously suppress the occurrence of poor display, which can form a more conventional A higher-brightness colored layer.

In addition, in Example IV-29 of Table 20, if the blue color material is combined with the above-mentioned specific yellow color material in PG59, and PG7 is further combined, compared to Example IV-28 that achieves the same hue, the above The P/V ratio is reduced, and the brightness 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 as in the examples, if PG58 is used, when y=0.670, the area of x=0.210 can be displayed. , But poor display occurs, and its brightness is worse than when PG59 is used. In addition, development residue or development adhesion also deteriorated. Also, as shown in Comparative Example IV-C2, even if the blue color material and the specific yellow color material are combined as in the examples, if PG36 is used, when y=0.670, the area of x=0.210 can be displayed, but Poor display occurs and the brightness is low. Moreover, even if the dispersant is combined with a polymer having a structural unit represented by the general formula (I), the dispersibility is still poor, so the contrast is low, and the resolubility, development residue, and development adhesion are also deteriorated.

Furthermore, on the other hand, in PG59, a blue color material is combined with a specific yellow color material, and then a urethane-based dispersant or a polyester-based dispersant is combined with Comparative Examples IV-C3~IV-C4 Photosensitive colored resin composition for color filters, due to its dispersibility Due to deterioration, the brightness is lower than that of the examples, and the contrast is low, and the resolubility and development residue are also deteriorated.

As shown in Comparative Examples IV-C5, IV-C7 and IV-C10 in Table 19, in the composition using G58, no blue color material combined, and yellow color material combined, the film thickness cannot be adjusted to 2.8μm, and x= A photosensitive colored resin composition with a chromaticity of 0.200 and y=0.710. In addition, in the combination of the color materials of Comparative Examples IV-C8 and IV-C9, it was not possible to prepare a photosensitive colored resin composition with a film thickness of 2.8 μm and a chromaticity of x=0.200 and y=0.710.

As shown in Comparative Example IV-C6, if the green color material is not used, and the blue color material is combined with the yellow color material, a chromaticity of 2.8μm, x=0.200, y=0.710 can be achieved, and no display failure occurs. However, Comparative Example IV-C6, which has more blue color materials, has significantly deteriorated brightness to the point where it cannot reach a practical level.

Claims (26)

A color material dispersion liquid for color filters, which is a color material dispersion liquid containing a color material, a dispersant, and a solvent; it is characterized in that: the color material contains CI Pigment Green 59; the dispersant system has the following general formula (I ) Is a polymer of the constituent unit; at least a part of the terminal nitrogen site of the constituent unit represented by the above general formula (I) is selected from the group consisting of compounds represented by the following general formulas (1) to (3) More than one compound of the group forms a salt;

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bonding group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, and R ² and R ^{3 are} also Can be bonded to each other to form a ring structure);

(In the general formula (1), Ra ^{represents a} linear, branched or cyclic alkyl group with 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a phenyl group or a benzyl group which may also have substituents, or a connection via an alkylene group with 1 to 4 carbons (meth) Bingxi Xi group; general formula (2), R ^b, R ^{b 'and} R ^{b "each} independently represent a hydrogen atom, an acidic group or an ester thereof, may have a substituent group of carbon number of 1 to 20 Linear, branched or cyclic alkyl, vinyl which may have substituents, phenyl or benzyl which may also have substituents, or -OR ^f , R ^f represents the number of carbons which may also have substituents 1-20 linear, branched or cyclic alkyl groups, vinyl groups that may also have substituents, phenyl or benzyl groups that may also have substituents, or linked via alkylene groups with 1 to 4 carbon atoms X represents a chlorine atom, a bromine atom or an iodine atom; in the general formula (3), R ^c and R ^d independently represent a hydrogen atom, a hydroxyl group, a straight chain with 1 to 20 carbon atoms, Branched or cyclic alkyl, vinyl, optionally substituted phenyl or benzyl, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons , Vinyl, phenyl or benzyl which may also have substituents, or (meth)acrylic groups linked via alkylene groups with 1 to 4 carbon atoms; wherein at least one of ^{R c} and R ^{d contains carbon} atom). The color material dispersion liquid for color filters according to claim 1, wherein the dispersant is a block copolymer having a structural unit represented by the general formula (I), and the amine value of the block copolymer is 40 mgKOH/g Above and below 130mgKOH/g. The color material dispersion liquid for color filters according to claim 1, wherein the dispersing agent has an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxyl group-containing monomer Block copolymers of segments. The color material dispersion liquid for color filters according to claim 1, wherein the glass transition temperature of the dispersant is 30°C or higher. According to claim 1 or 2, the color material dispersion liquid for color filters, wherein the color material contains C.I. Pigment Green 59 and a yellow color material. According to claim 5, the color material dispersion liquid for color filters, wherein the color material contains 5-95% by mass of the C.I. Pigment Green 59. The color material dispersion liquid for color filters of claim 5, wherein the yellow color material is selected from CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 185, CI Pigment Yellow 150 and its derivative pigments One or more of the group. The color material dispersion liquid for color filters of claim 5, wherein the yellow color material is a derivative pigment of CI Pigment Yellow 150, and the derivative pigment of CI Pigment Yellow 150 is the following chemical formula (i) or following it Metal complexes of mono-, di-, tri-, and tetra-anions of an azo compound, which is one of the tautomeric structures, and metal, and include Ni and Zn, or Ni and Cu as the above-mentioned metal;

(In the above chemical formula (i), R is each independently OH, NH ₂ , NH-CN, acylamino or arylamino, and R'is independently -OH or -NH ₂ ). According to claim 5, the color material dispersion liquid for color filters, wherein the color material further includes at least one of C.I. Pigment Green 58 and C.I. Pigment Green 7. The color material dispersion liquid for color filters of claim 1 or 2, wherein the color material includes CI pigment green 59, blue color material and yellow color material, and the yellow color material series (Y1) contains CI pigment yellow 185 At least one yellow color material; or (Y2) with CI Pigment Yellow 139 as an essential ingredient, and further containing at least two types selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150 and their derivative pigments yellow Color material. According to claim 10, the color material dispersion liquid for color filters, wherein the blue color material includes at least one of C.I. Pigment Blue 15:3 and C.I. Pigment Blue 15:4. A photosensitive colored resin composition for color filters, which contains color materials, dispersants, alkali-soluble resins, multifunctional monomers, photoinitiators, and solvents; and is characterized in that: the color materials include CI pigment green 59; The above-mentioned dispersant is a polymer having a structural unit represented by the following general formula (I);

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, A represents a divalent bonding group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, and R ² and R ^{3 are} also Can be bonded to each other to form a ring structure). The photosensitive colored resin composition for color filters according to claim 12, wherein the dispersant is a block copolymer having a structural unit represented by the general formula (I), and the amine value of the block copolymer is 40 mgKOH /g or more and 130mgKOH/g or less. The photosensitive colored resin composition for a color filter according to claim 12 or 13, wherein, in the dispersant, at least a part of the terminal nitrogen portion of the structural unit represented by the general formula (I) is selected from One or more compounds of the group consisting of compounds represented by the following general formulas (1) to (3) form a salt;

(In the general formula (1), Ra ^{represents a} linear, branched or cyclic alkyl group with 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a phenyl group or a benzyl group which may also have substituents, or a connection via an alkylene group with 1 to 4 carbons (meth) Bingxi Xi group; general formula (2), R ^b, R ^{b 'and} R ^{b "each} independently represent a hydrogen atom, an acidic group or an ester thereof, may have a substituent group of carbon number of 1 to 20 Linear, branched or cyclic alkyl, vinyl which may have substituents, phenyl or benzyl which may also have substituents, or -OR ^f , R ^f represents the number of carbons which may also have substituents 1-20 linear, branched or cyclic alkyl groups, vinyl groups that may also have substituents, phenyl or benzyl groups that may also have substituents, or linked via alkylene groups with 1 to 4 carbon atoms X represents a chlorine atom, a bromine atom or an iodine atom; in the general formula (3), R ^c and R ^d independently represent a hydrogen atom, a hydroxyl group, a straight chain with 1 to 20 carbon atoms, Branched or cyclic alkyl, vinyl, optionally substituted phenyl or benzyl, or -OR ^e , R ^e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons , Vinyl, phenyl or benzyl which may also have substituents, or (meth)acrylic groups linked via alkylene groups with 1 to 4 carbon atoms; wherein at least one of ^{R c} and R ^{d contains carbon} atom). Photosensitive colored resin for color filter as claimed in claim 14 A composition, wherein the dispersant system has a block copolymer comprising an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxyl group-containing monomer. The photosensitive colored resin composition for color filters according to claim 14, wherein the glass transition temperature of the dispersant is 30°C or higher. The photosensitive colored resin composition for color filters of claim 12 or 13, wherein the color material contains C.I. Pigment Green 59 and a yellow color material. The photosensitive colored resin composition for color filters according to claim 17, wherein the color material contains 5 to 95% by mass of the C.I. Pigment Green 59. The photosensitive colored resin composition for color filters according to claim 17, wherein the yellow color material is selected from CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 185, CI Pigment Yellow 150 and its derivative pigments One or more types of the group. The photosensitive colored resin composition for color filters of claim 17, wherein the yellow color material is a derivative pigment of CI Pigment Yellow 150, and the derivative pigment of CI Pigment Yellow 150 is the following chemical formula (i) or Metal complexes of mono-, di-, tri-, and tetra-anions of an azo compound following one of its tautomeric structures and metals, and containing Ni and Zn, or Ni and Cu as the aforementioned metals;

(In the above chemical formula (i), R is independently OH, NH ₂ , NH-CN, an amide group or arylamino group, and R'is independently -OH or -NH ₂ ). The photosensitive colored resin composition for a color filter according to claim 17, wherein the color material further includes at least one of C.I. Pigment Green 58 and C.I. Pigment Green 7. The photosensitive colored resin composition for color filters of claim 12 or 13, wherein the color material includes CI pigment green 59, a blue color material, and a yellow color material, and the yellow color material series (Y1) contains CI pigment yellow 185 at least one yellow color material; or (Y2) with CI Pigment Yellow 139 as an essential component, and further containing at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 150 and their derivative pigments 2 kinds of yellow color materials. According to claim 22, the photosensitive colored resin composition for a color filter, wherein the blue color material includes at least one of C.I. Pigment Blue 15:3 and C.I. Pigment Blue 15:4. A color filter comprising at least a transparent substrate and a coloring layer provided on the transparent substrate, characterized in that at least one of the coloring layers has a color filter belonging to any one of claims 12 to 23 The colored layer of the hardened material of the photosensitive colored resin composition for the sheet. A liquid crystal display device having the color filter described in claim 24, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. An organic light-emitting display device having the color filter and an organic light-emitting body described in claim 24.

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