JP6494875B2 - Color material dispersion for color filter, colored resin composition for color filter, color filter, and display device - Google Patents

Description

  The present invention relates to a color filter color material dispersion, a color filter colored resin composition, a color filter, and a display device.

  In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (cell phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.

  Many conventional display devices comply with sRGB (IEC 61966-2-1), which is an international standard for color space. However, in order to obtain an expression closer to the real thing, in order to further improve color reproducibility, compared to sRGB, AdobeRGB having a wide color gamut, DCI (Digital Cinema Initiates) having a wide color gamut, and BT (Broadcasting Service Television). The demand for display devices corresponding to 2020 is increasing.

Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. As a light source at that time, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. In the organic light emitting display device, a color filter is used for color adjustment.
For this reason, there is an increasing demand for color filters with higher brightness, higher contrast, and improved color reproducibility.

In the color filter, a region connecting three points of red, green, and blue pixels is a limit of colors that can be reproduced. In other words, a color filter having a larger triangle formed by three points of red, green, and blue pixels has a wider range of colors that the display device can reproduce on the screen.
Therefore, in order to achieve a color space having a wide color gamut, it is required to achieve high color density chromaticity in each color pixel.

  In Patent Document 1, as a color filter used in a liquid crystal display device of a white LED light source having a color gamut that satisfies the NTSC standard, the transmittance at 550 nm that transmits blue pixels in the color filter is 1% or less, and A color filter having a maximum transmittance wavelength of visible light transmitting through the color filter in the range of 470 nm to 500 nm is disclosed, and the blue coloring composition forming the blue pixel is C.I. I. Pigment Blue 15: 6 or C.I. I. Pigment Blue 15: 3 at least one blue pigment; I. Pigment Green 7, C.I. I. Pigment Green 36 and C.I. I. Pigment Green 58 contains at least one green pigment.

JP 2012-220817 A

In order to achieve a high color density in a blue pixel, if the density of the blue color material in the pixel is increased, the solvent re-solubility is greatly deteriorated, causing a problem.
That is, in the manufacturing process of a color filter, it is calculated | required that the solid content of the colored resin composition once dried is excellent in the property which melt | dissolves in a solvent again, and the re-solubility in a solvent. For example, if a colored resin composition adheres to the tip of the die lip when coating with a die coater, a solidified product is generated by drying, but when the coating is resumed, the solidified product is not likely to dissolve in the colored resin composition. The solidified material on the die lip is partly peeled off and easily adheres to the colored layer of the color filter, causing a foreign matter defect. In particular, when the colorant concentration of the colored resin composition is increased, the solvent re-solubility is likely to be insufficient, and the yield is reduced due to the occurrence of the foreign matter in the color filter manufacturing process.
It is presumed that the blue color material used for the blue pixel of the color filter is generally caused by the tendency that the solvent resolubility tends to be very poor.
Further, even the colored resin composition according to the technique of Patent Document 1 has a problem that the solvent re-solubility is poor.

  The present invention provides a color material dispersion for a color filter that is excellent in color material dispersion stability, has improved solvent resolubility, and can form a colored resin composition that expands the blue reproduction range, and the color material dispersion for the color filter. A color resin composition for a color filter that can form a colored layer with improved solvent resolubility and an expanded blue reproduction range, and color reproducibility using the color resin composition for color filter. An object is to provide a color filter that is excellent in productivity and a display device that is excellent in color reproducibility and improved in productivity by using the color filter.

A color material dispersion for a color filter according to the present invention is a color material dispersion containing a color material, a dispersant, and a solvent,
The color material is a blue color material, a purple color material, and C.I. I. Including Pigment Green 59,
The dispersing agent is a color material dispersion for a color filter, which is a polymer having a structural unit represented by the following general formula (I).

The colored resin composition for a color filter according to the present invention is a colored resin composition for a color filter containing a coloring material, a dispersant, a binder component, and a solvent,
The color material is a blue color material, a purple color material, and C.I. I. Including Pigment Green 59,
The dispersant is a colored resin composition for a color filter, which is a polymer having a structural unit represented by the following general formula (I).

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａは、２価の連結基、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２及びＲ^３が互いに結合して環構造を形成してもよい。）

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R ² and R ³ may combine with each other to form a ring structure.)

  The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a colored resin composition for a color filter according to the present invention. It is the coloring layer which is a hardened | cured material of this.

  The present invention provides a display device comprising the color filter according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the color material dispersion liquid for color filters which can form the colored resin composition which is excellent in color material dispersion stability, improves solvent re-dissolution property, and expands a blue reproduction range, the said color for color filters Color reproducibility using a colored dispersion composition for a color filter that can form a colored layer with improved solvent resolubility and an expanded blue reproduction range, using the material dispersion, and the color resin composition for color filter By using a color filter that is excellent in productivity and improved in productivity and the color filter, a display device that is excellent in color reproducibility and improved in productivity can be provided.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the display device of the present invention. FIG. 3 is a schematic view showing another example of the display device of the present invention.

Hereinafter, the color filter color material dispersion, the color filter colored resin composition, the color filter, and the display device according to the present invention will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In addition, C.I. I. Pigment Blue “PB”, C.I. I. Pigment Violet “PV”, C.I. I. Pigment Green is abbreviated as “PG” where appropriate.

[Colorant dispersion]
A color material dispersion for a color filter according to the present invention is a color material dispersion containing a color material, a dispersant, and a solvent,
The color material is a blue color material, a purple color material, and C.I. I. Including Pigment Green 59,
The dispersant is a polymer having a structural unit represented by the following general formula (I).

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基、Ａは、２価の連結基、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２及びＲ^３が互いに結合して環構造を形成してもよい。）

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R ² and R ³ may combine with each other to form a ring structure.)

Since the color material dispersion of the present invention is used in combination with the specific color material and a polymer having a structural unit represented by the general formula (I) as a dispersant, the color material dispersion stability is improved. It is possible to form a colored resin composition that is excellent, has improved solvent resolubility, and expands the blue reproduction range.
Although the cause of the blue color material is not yet known, the solvent resolubility tends to be poor, and when the colorant concentration is increased, the solvent resolubility tends to be very poor. Further, even if the color material concentration is increased by using a blue color material, there is a limit to the expansion of the blue reproduction range, which is insufficient. As in Patent Document 1, when a blue color material and a green color material are mixed, chromaticity with a high color density may be achieved, but the solvent resolubility is poor. In order to achieve a high color density chromaticity by mixing a blue color material and a green color material, it is necessary to increase the color material concentration in the composition considerably, resulting in poor solvent resolubility. It is estimated to be.
On the other hand, in the color material dispersion of the present invention, a blue color material, a purple color material, and C.I. I. CI Pigment Green 59 is used in combination with a dispersant that is a polymer having a specific structural unit represented by the general formula (I).
C. used as a coloring material in the present invention. I. Pigment Green 59 (hereinafter sometimes abbreviated as PG59) has a single color and a bluish green color, has a relatively strong coloring power, and has a high luminance. If a violet color material is further combined with such a combination of PG59 and a blue color material, the P / V ratio ((the total color material in the composition can be reduced) even if the content of the blue color material in the color material is suppressed. It was found that even when the ratio of (mass) / (total mass of solids other than coloring materials in the composition) ratio) was suppressed, a blue pixel contained in the blue chromaticity region of the high color density could be produced. Therefore, it is suitably used as a blue color material dispersion. Further, when a blue pixel is produced using PG59, the luminance tends to be higher than when a blue pixel is produced using PG58.
Further, since the polymer having the structural unit represented by the general formula (I) is combined as a dispersant with the combination of the specific color materials, the specific color material is represented by the general formula (I), respectively. It is presumed that the specific color material that is firmly adsorbed to the nitrogen site contained in the structural unit and is well dispersed and surrounded by the dispersant is likely to flow while adsorbed to the re-dissolvable solvent.
A colored resin composition for producing a blue pixel included in a blue chromaticity region having a high color density is prepared by suppressing the content of the blue color material in the color material and suppressing the P / V ratio. And also has the function of the specific dispersant. By these things, it is estimated that the colored resin composition with improved solvent re-solubility can be formed.
Furthermore, since the total content of the color material components in the colored resin composition for producing a blue pixel included in the blue chromaticity region of high color density can be suppressed, the content of the binder component is relatively Since it can be increased, the plate-making property is improved, and development chipping is easily suppressed. On the other hand, development residue is easily suppressed, and adhesion to the substrate is improved.

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

<Color material>
In the present invention, the color material is a blue color material, a purple color material, and C.I. I. Pigment Green 59 is included.
C. I. Pigment Green 59 (PG59) is a zinc phthalocyanine pigment.
PG59 displays x = 0.10 or more and 0.30 or less, and y = 0.30 or more and 0.64 or less as chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source alone. It is a color material that can display x = 0.13 or more and 0.20 or less, and y = 0.32 or more and 0.60 or less.

The PG 59 is characterized in that it can display an xy chromaticity coordinate area surrounded by the following equations 1, 2, and 3 in the XYZ color system of JIS Z8701 measured by using a C light source alone.
(Equation 1)
y = 6.715 × x-0.286
However, 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
However, 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
However, in Equation 3, 0.121 <x <0.310

  Among the xy chromaticity coordinate regions surrounded by the equations 1, 2, and 3, the region having x = 0.13 to 0.20 and y = 0.32 to 0.60 is the most characteristic and effective. is there.

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

In order to measure the color of PG59 by coating it alone, prepare a coating solution by blending PG59 with an appropriate dispersant, binder component and solvent, apply it on a transparent substrate and dry it. It may be cured accordingly. As a binder component, a non-curable thermoplastic resin composition may be used as long as a transparent coating film capable of performing colorimetry can be formed, or a photo-curable (photosensitive) or thermosetting resin composition. May be used. Moreover, in the 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 colorimetry can be performed. Specifically, for example, solid components other than the coloring material used in the resin composition of Example 1 described later can be used as the binder component.
As a transparent coating film that can perform colorimetry, including a dispersant and a binder component, for example, the film thickness is 2.0 μm, and the transmittance of the spectral transmittance spectrum at 380 nm to 780 nm is 95% or more. Can be.
The spectral transmittance spectrum can be measured using a spectroscopic measurement device (for example, an Olympus microspectrophotometer OSP-SP200).
PG59 has a single color and bluish green, has a relatively strong coloring power, and has a high luminance. Furthermore, PG59 tends to have better dispersibility than PG7, which is a conventional green pigment, and tends to improve contrast, and tends to have good re-dissolvability.

Further, as a blue color material used in the present invention, when a 2.5 μm coating film is formed at P / V = 0.2 and a spectral transmittance spectrum is measured, a 440 nm transmittance is 60% or more and a 520 nm transmittance is obtained. A colorant having a rate of 10% or more and a 580 nm transmittance of less than 10% is used.
Note that the color measurement can be performed by forming a blue color material into a single film in the same manner as PG59 described above.

  The blue color material used in the colored resin composition for a color filter of the present invention is not particularly limited, and a known blue organic pigment, a blue dye, and a blue lake color material that is a salt-forming compound of a blue dye are used. Can do. Here, the blue organic pigment is excellent in various resistances such as heat resistance and light resistance compared to the dye and the lake color material, and the blue dye is soluble and therefore has a higher transmittance than the organic pigment. In addition, since the lake color material is derived from a dye, it has a higher transmittance than a normal pigment and can achieve the demand for higher brightness.

  Examples of the blue organic pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. And CI Pigment Blue 60. Among these, a copper phthalocyanine-based blue pigment is preferable from the viewpoint of relatively excellent luminance.

  Examples of the blue dye include methine dyes, anthraquinone dyes, azo dyes, triarylmethane dyes, and phthalocyanine dyes.

In the blue lake color material which is a salt forming compound of the blue dye, the counter ion differs depending on the kind of the dye, the counter ion of the acidic dye is a cation, and the counter ion of the basic dye is an anion.
Examples of the counter cation of the acid dye include an ammonium cation, a metal cation, and an inorganic polymer.
As a rake agent that generates ammonium ions, for example, primary amine compounds, secondary amine compounds, tertiary amine compounds, and the like are preferable. Among them, secondary amines are preferred because of their excellent heat resistance and light resistance. It is preferable to use an amine compound or a tertiary amine compound.
Moreover, what is necessary is just to select suitably from the metal salt which has a desired metal ion as a lake agent which generate | occur | produces a metal cation.
The counter cation of the acid dye can be used alone or in combination of two or more.

On the other hand, the counter anion of the basic dye may be an organic anion or an inorganic anion. Examples of the organic anion include organic compounds having an anionic group as a substituent.
Moreover, you may use a well-known acidic dye as an organic anion. In this case, the lake color material is an acid dye and a basic dye present as an ion pair. Examples of rake agents that generate these organic anions include alkali metal salts and alkaline earth metal salts of the above organic anions.
On the other hand, examples of the inorganic anion include an oxo acid anion (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ²⁻ ), molybdate ion (MoO ₄ ²⁻ ), and the like) Mention may be made of inorganic anions such as polyacid anions condensed with oxo acids and mixtures thereof.
The polyacid may be an isopolyacid anion (M _m O _n ) ^c- or a heteropoly acid anion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co.
Among these, from the viewpoint of heat resistance, a polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polyacid anion containing at least tungsten is more preferable.
Examples of rake agents that generate inorganic anions include alkali salts and alkali metal salts of the above inorganic anions.
The counter anion of the basic dye in the lake color material can be used alone or in combination of two or more.

  Examples of blue rake color materials include C.I. I. Pigment blue 1, C.I. I. Pigment blue 1: 2, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 8, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 12, C.I. I. Pigment blue 14, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 18, C.I. I. Pigment blue 19, C.I. I. Pigment blue 24, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 53, C.I. I. Pigment blue 56, C.I. I. Pigment blue 56: 1, C.I. I. Pigment blue 61, C.I. I. Pigment blue 61: 1, C.I. I. Pigment blue 62, C.I. I. Pigment blue 63, C.I. I. And CI Pigment Blue 78.

The blue dye and the blue lake color material are not particularly limited, but among them, a triarylmethane color material containing triarylmethane as a basic skeleton is preferable from the viewpoint of improving the brightness and contrast of the colored layer.
Examples of the triarylmethane blue color material include a triarylmethane dye having a triarylmethane skeleton represented by the following general formula (1) and a triarylmethane lake color material.

（一般式（１）中、Ｒ^ｉ〜Ｒ^ｖｉは各々独立に水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表し、Ｒ^ｉとＲ^ｉｉ、Ｒ^ｉｉｉとＲ^ｉｖ、Ｒ^ｖとＲ^ｖｉが結合して環構造を形成してもよい。Ａｒ^ｉは置換基を有していてもよい２価の芳香族基を表す。複数あるＲ^ｉ〜Ｒ^ｖｉ及びＡｒ^ｉはそれぞれ同一であっても異なっていてもよい。）

(In the general formula (1), R ^{i to} R ^vi each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁱ and R ⁱⁱ , R ⁱⁱⁱ and R ^iv , R ^v and R ^vi may combine to form a ring structure, and Ar ⁱ represents a divalent aromatic group which may have a substituent. ^{i to} R ^vi and Ar ⁱ may be the same or different.)

In the general formula (1), the alkyl group in R ^{i to} R ^vi is not particularly limited, and examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms. Is preferably a straight chain or branched alkyl group having 8 carbon atoms, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms from the viewpoint of ease of production and raw material procurement. Groups and methyl groups are preferred. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group.
The aryl group in R ^{i to} R ^vi is not particularly limited, and examples thereof include an aryl group having 6 to 12 carbon atoms, and specific examples include a phenyl group and a naphthyl group. Examples of the substituent that the aryl group may have include an alkyl group and a halogen atom.
R ⁱ and R ⁱⁱ , R ⁱⁱⁱ and R ^iv , R ^v and R ^vi are bonded to form a ring structure. R ⁱ and R ⁱⁱ , R ⁱⁱⁱ and R ^iv , R ^v and R ^vi are nitrogen A ring structure is formed through an atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Divalent aromatic group in Ar ⁱ is not particularly limited, other aromatic hydrocarbon radical consisting of carbon ring may be a heterocyclic group. As an aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to a benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, Examples thereof include chain polycyclic hydrocarbons such as diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton such as diphenyl ether. On the other hand, the heterocyclic ring in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; And condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups may have a substituent.
Examples of the substituent that the aromatic group may have include an alkyl group having 1 to 5 carbon atoms and a halogen atom.
Ar ⁱ is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group composed of a condensed polycyclic carbocyclic ring having 10 to 14 carbon atoms, particularly a phenylene group or a naphthylene group. It is preferable.
In addition, a plurality of R ^{i to} R ^vi and Ar ⁱ in one molecule may be the same or different.

  Specific examples of the triarylmethane dye represented by the general formula (1) include Basic Blue 7 and Basic Blue 26.

In addition, as the triarylmethane-based lake color material, one or a plurality of elements selected from molybdenum, tungsten, silicon, and phosphorus of the basic triarylmethane-based dye represented by the general formula (1) And the rake color material which consists of an anion which contains oxygen as an essential element is used suitably from the point which achieves the high brightness | luminance of a colored layer. The anion is preferably a heteropolyacid or isopolyacid anion containing at least one of molybdenum and tungsten as an essential element. Among these, one or more selected from the group consisting of phosphotungstic acid, silicotungstic acid, phosphotungstomolybdic acid, and cytungstomolybdic acid is preferably used.
As the anion, among _{its, (PMo x W 12-x} O 40) 3- / 3 ( where, x = 1, 2, or 3 of an ^{_{integer), (SiMoW 11 O 40)}} 4- / 4, _{(P 2 Mo y W 18-} y O 62) 6- / 6 ( where, y = 1, 2, or 3 of an integer) is preferably used. ^{_{(SiMoW 11 O 40) 4- /}} 4 and _{(P 2 Mo y W 18-} y O 62) 6- / 6 ( where, y = 1, 2, or 3 of an integer) is used at least one of Is preferable from the viewpoint of improving heat resistance.
Such rake color materials can be prepared with reference to, for example, International Publication No. 2012/039416 and International Publication No. 2012/039417.

  Moreover, as a triarylmethane type | system | group lake color material, what is represented by following General formula (2) is used suitably from the point which achieves the high brightness | luminance of a colored layer.

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

(In General Formula (2), A is an a-valent organic group in which the carbon atom directly bonded to N does not have a π bond, and the organic group is saturated aliphatic carbonized at least at the terminal directly bonded to N. It represents an aliphatic hydrocarbon group having a hydrogen group or an aromatic group having the aliphatic hydrocarbon group, and O, S, and N may be contained in the carbon chain, and B ^c- represents a c-valent anion. R ^{XI to} R ^XV each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and R ^XII , R ^XIII , R ^XIV and good .Ar ¹ be R ^XV combine to form a ring structure represents a divalent aromatic group which may have a substituent. plural ^R XI ^{to R XV} and Ar ¹ each identical It may or may not be.
a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

A in the general formula (2) is an a-valent organic group in which the carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group is saturated at least at the terminal directly bonded to N. Represents an aliphatic hydrocarbon group having an aromatic hydrocarbon group, or an aromatic group having the aliphatic hydrocarbon group, and includes O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain It may be. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as the color tone and transmittance of the cationic coloring portion are not affected by the linking group A and other coloring portions, Similar colors can be retained.
In A, an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N is linear, branched or cyclic unless the terminal carbon atom directly bonded to N has a π bond. The carbon atom other than the terminal may have an unsaturated bond, may have a substituent, and the carbon chain contains O, S, and N. Also good. For example, a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.
The aromatic group having an aliphatic hydrocarbon group in A is a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. And may have a substituent, and may be a heterocyclic ring containing O, S, and N.
Especially, it is preferable that A contains a cyclic | annular aliphatic hydrocarbon group or an aromatic group from the point of the robustness of frame | skeleton.
Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of skeleton fastness. The bridged alicyclic hydrocarbon group means a polycyclic aliphatic hydrocarbon group having a bridged structure in the aliphatic ring and having a polycyclic structure, for example, norbornane, bicyclo [2,2,2]. Examples include octane and adamantane. Among the bridged alicyclic hydrocarbon groups, norbornane is preferable. Moreover, as an aromatic group, the group containing a benzene ring and a naphthalene ring is mentioned, for example, Among these, the group containing a benzene ring is preferable. For example, when A is a divalent organic group, a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group substituted with 2 alkylene groups having 1 to 20 carbon atoms such as a xylylene group Etc.

  The valence a in A is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more. In this lake color material, since the cation valence a is 2 or more, it is excellent in heat resistance, and among them, the cation valence a is preferably 3 or more. The upper limit of a is not particularly limited, but a is preferably 4 or less, and more preferably 3 or less, from the viewpoint of ease of production.

Specific examples of Ar ¹ and R ^{XI to} R ^{XV in} the general formula (2) include those described in International Publication No. 2012/144520 pamphlet.

In the rake color material represented by the general formula (2), the anion portion (B ^c− ) is not particularly limited, and may be an organic anion or an inorganic anion. Here, the organic anion represents an anion containing at least one carbon atom. Moreover, an inorganic anion represents the anion which does not contain a carbon atom. In the present invention, B ^c- is preferably an inorganic anion from the viewpoint of high brightness and excellent heat resistance.
Specific examples of the organic anion and the inorganic anion include those described in International Publication No. 2012/144520 pamphlet.
Especially, it is preferable that it is an anion of the inorganic acid containing at least 1 sort (s) of tungsten (W) and molybdenum (Mo) from the point which is excellent in heat resistance with high brightness | luminance.

  In the general formula (2), b represents the number of cations, d represents the number of anions in the molecular aggregate, and b and d represent an integer of 1 or more. When b is 2 or more, a plurality of cations in the molecular aggregate may be one kind alone, or two or more kinds may be combined. When d is 2 or more, the anion present in the molecular aggregate may be a single anion or a combination of two or more, and an organic anion and an inorganic anion may be used in combination. .

E in the general formula (2) is an integer of 0 or 1. e = 0 represents a triarylmethane skeleton, and e = 1 represents a xanthene skeleton. A plurality of e may be the same or different. In the rake colorant represented by the general formula (2) used in the present invention, those containing at least a triarylmethane skeleton are preferably used.
In addition, as a rake color material represented by General formula (2), it can prepare with reference to international publication 2012/144520 pamphlet, for example.

Examples of the blue color material include C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 15: 3, C.I. I. It is preferable from the point of hue that it is 1 or more types selected from the group which consists of pigment blue 15: 4 and a triarylmethane type | system | group lake color material.
Examples of the blue color material include C.I. I. Pigment Blue 16 is preferable from the viewpoint of expanding the hue, particularly the color reproduction range. C. I. Since the pigment blue 16 has a strong coloring power and can lower the P / V ratio, the platemaking property is improved, development chipping is easily suppressed, while development residue is easily suppressed, and adhesion to the substrate is improved. Is improved.

Moreover, as a purple color material used in the present invention, when a 2.5 μm coating film is formed at P / V = 0.2 and a spectral transmittance spectrum is measured, a 440 nm transmittance is 40% or more and a 520 nm transmittance is obtained. A colorant having a rate of less than 10% and a transmittance of 680 nm of 40% or more is used.
The purple color material used in the present invention includes a red purple color material to which the name of a red dye is attached.
In addition, it can perform like the above-mentioned PG59 to make a purple color material into a coating film, and to measure a color.

  It does not specifically limit as a purple color material used for the colored resin composition for color filters of this invention, A well-known purple organic pigment, a purple dye, a purple lake color material, etc. can be used.

  Examples of the purple organic pigment include C.I. I. Pigment violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38 and the like. Among these, Pigment Violet 23 is preferable from the viewpoint of relatively excellent coloring power.

  Examples of the purple dye include C.I. I. Acid Violet 29, 31, 33, 34, 36, 36: 1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, 126 and other anthraquinone acid dyes, C.I. I. Cyanine acid dyes such as Basic Red 12; triarylmethane acid dyes such as Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72; I. Acid Red 289, C.I. I. Acid Violet 9, C.I. I. Rhodamine acid dyes such as Acid Violet 30; I. Triarylmethane basic dyes such as basic violet 1, 3, and 14; I. And xanthene-based basic dyes such as Basic Violet 11.

Examples of the purple lake color material include those obtained by rakeizing the above purple dye with a lake agent.
In the lake color material, the counter ion differs depending on the kind of the dye, the counter ion of the acidic dye is a cation, and the counter ion of the basic dye is an anion. The counter cation of the acid dye and the counter anion of the basic dye may be the same as those mentioned as the blue dye.

  The purple lake color material is preferably one or more selected from the group consisting of an anthraquinone color material, a cyanine color material, and a xanthene color material.

Moreover, as the purple dye and the purple lake color material, a xanthene color material containing xanthene as a basic skeleton and including a rhodamine color material is preferable from the viewpoint of improving the luminance and contrast of the colored layer.
As the xanthene acid dye in the lake color material, it is preferable to have a compound represented by the following general formula (3), that is, a rhodamine acid dye.

（一般式（３）中、Ｒ^ａ〜Ｒ^ｄは、それぞれ独立に、水素原子、アルキル基、アリール基、又はヘテロアリール基を表し、Ｒ^ａとＲ^ｂ、Ｒ^ｃとＲ^ｄが結合して環構造を形成してもよい。Ｒ^ｅは、酸性基、Ｘは、ハロゲン原子を表す。ｍは０〜５の整数を表す。一般式（３）は酸性基を１個以上有するものであり、ｎは０以上の整数である。）

(In General Formula (3), R ^{a to} R ^d each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R ^a and R ^b , R ^c and R ^d are bonded to each other. good .R ^e to form a ring structure, an acidic group, X is, .m represents a halogen atom is an integer of 0 to 5. general formula (3) are those having at least one acidic group , N is an integer of 0 or more.)

The alkyl group in R ^{a to} R ^d is not particularly limited. Examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. More preferably, it is a linear or branched alkyl group having 1 to 5 carbon atoms. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and the like, and the substituted alkyl group includes a benzyl group, and further, a substituent. May have a halogen atom or an acidic group.
The aryl group in R ^{a to} R ^d is not particularly limited. For example, the aryl group which may have a C6-C20 substituent is mentioned, Especially, group which has a phenyl group, a naphthyl group, etc. is preferable. Examples of the heteroaryl group in R ^{a to} R ^d include a heteroaryl group which may have a substituent having 5 to 20 carbon atoms, and a hetero atom containing a nitrogen atom, an oxygen atom, or a sulfur atom is preferable. .
Examples of the substituent that the aryl group or heteroaryl group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, a carbamoyl group, and a carboxylic acid ester group. .
R ^{a to} R ^d may be the same or different.

Specific examples of the acidic group or a salt thereof include a carboxy group (—COOH), a carboxylate group (—COO ⁻ ), a carboxylate group (—COOM, where M represents a metal atom), a sulfonate group (—SOO). ₃ ^-), a sulfo group _(-SO 3 H), sulfonate _(-SO 3 M, wherein M represents a metal atom), and among them, a sulfonato group (-SO ₃ ^-.), a sulfo group It is preferable to have at least one of (—SO ₃ H) or a sulfonate group (—SO ₃ M). Examples of the metal atom M include a sodium atom and a potassium atom.

As the compound represented by the general formula (3), Acid Red 289, Acid Violet 9, Acid Violet 30 and the like are preferable from the viewpoint of increasing luminance.
Further, from the viewpoint of heat resistance, a compound having a betaine structure in which m = 1 and n = 0 in general formula (3) is preferable.
Among them, m = 1 and n = 0, R ^a and R ^c are each independently an alkyl group or an aryl group, and R ^b and R ^d are each independently an aryl group or a heteroaryl group. It is preferable from the viewpoint that a colored layer excellent in luminance and light resistance can be formed.
Although the manufacturing method of the compound represented by the said General formula (3) is not specifically limited, For example, it can obtain by referring to Unexamined-Japanese-Patent No. 2010-211198.

  A metal lake color material is suitably used as the lake color material of the xanthene acid dye. A metal lake color material containing a metal atom is used as a rake agent. By using a rake agent containing a metal atom, the heat resistance of the coloring material is increased. As such a rake agent, a rake agent containing a metal atom that becomes a divalent or higher valent metal cation is preferable.

  In the color material dispersion of the present invention, a blue color material, a purple color material, and PG59 are used in combination as color materials, but other color materials as exemplified in the colored resin composition described below are combined. It may be used. As the other color material, for example, a red color material, an orange color material, a green color material, and the like are preferably used. Among them, a red color material, a green color, and the like exemplified in the colored resin composition described later from the viewpoint of hue. A material is preferably used.

  In the color material dispersion of the present invention, each content ratio of the blue color material, the purple color material, and PG59, and the content ratio when other color materials are used are the same content ratios as those of the colored resin composition described later. It is preferable to do. However, two or more colorant dispersions can be appropriately mixed and used to produce a colored resin composition, so that the colorant dispersion is preferably used even if the content ratio is not the same as that of the later-described colored resin composition.

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

Moreover, although the average dispersed particle diameter of the color material in the color material dispersion varies depending on the type of the color material used, it is preferably in the range of 10 nm to 100 nm, and preferably in the range of 15 nm to 60 nm. More preferred.
The average dispersed particle size of the color material in the color material dispersion is the dispersed particle size of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. For particle size measurement with a laser light scattering particle size distribution meter, the color material dispersion is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is a volume average particle size.

In the color material dispersion of the present invention, the content of the color material is not particularly limited. The content of the color material is 5 parts by mass or more and 80 parts by mass or less, more preferably 8 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the total solid content in the color material dispersion from the viewpoint of dispersibility and dispersion stability. It is preferable to mix | blend in the ratio below a mass part.
In particular, when forming a coating film or a colored layer having a high color material concentration, it is 30 parts by mass or more and 80 parts by mass or less, more preferably 40 parts by mass or more with respect to 100 parts by mass of the total solid content in the color material dispersion. It is preferable to mix | blend in the ratio of 75 mass parts or less.

<Dispersant>
In the present invention, a polymer having a structural unit represented by the general formula (I) is used as a dispersant. The structural unit represented by the general formula (I) has basicity and functions as an adsorption site for a coloring material.
The color material dispersion of the present invention uses a polymer having a structural unit represented by the general formula (I), thereby improving the adsorption performance to the color material and improving the dispersibility and dispersion stability of the color material. To do.

In general formula (I), A is a divalent linking group. Examples of the divalent linking group in A include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (-R ' -OR "-: R 'and R" each independently represents an alkylene group) and combinations thereof.
Among these, from the viewpoint of dispersibility, A in the general formula (I) is preferably a divalent linking group containing a —CONH— group or a —COO— group.

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

The phrase “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 through a nitrogen atom. The ring structure formed by R ² and R ³ may contain a hetero atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the present invention, among them, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ³ are bonded to form a pyrrolidine ring. , A piperidine ring and a morpholine ring are preferable, and among them, at least one of R ² and R ³ is an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ^3. Are preferably bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

Examples of the structural unit represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and other alkyl group-substituted amino groups. Examples include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and the like. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
The structural unit represented by the general formula (I) may be composed of one type or may include two or more types of structural units.

The polymer having the structural unit represented by the general formula (I) preferably further includes a portion having solvent affinity from the viewpoint of improving dispersibility. As the solvent affinity site, a monomer having an ethylenically unsaturated bond that can be polymerized with a monomer that derives the structural unit represented by the general formula (I) is selected depending on the solvent so as to have solvent affinity. It is preferable to select and use as appropriate. As a standard, it is preferable to introduce a solvent-affinity site so that the solubility of the polymer at 23 ° C. is 50 (g / 100 g solvent) or more with respect to the solvent used in combination.
As the polymer used in the present invention, among others, a block copolymer can be formed from the viewpoint that the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition can be improved and a colored layer having high brightness and high contrast can be formed. Or a graft copolymer is preferable and a block copolymer is particularly preferable. Hereinafter, particularly preferred block copolymers will be described in detail.

(Block copolymer)
When the block containing the structural unit represented by the general formula (I) is an A block, the structural unit represented by the general formula (I) is basic and the A block has an adsorption site for a coloring material Function as. On the other hand, the B block not containing the structural unit represented by the general formula (I) functions as a block having solvent affinity. In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.

  Examples of the structural unit constituting the B block include a monomer having an unsaturated double bond copolymerizable with the monomer that derives the structural unit represented by the general formula (I). The structural unit represented by (II) is preferred.

（一般式（ＩＩ）中、Ａ’は、直接結合又は２価の連結基、Ｒ^４は、水素原子又はメチル基、Ｒ^５は、炭化水素基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ−Ｒ^８又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素原子数１以上５以下のアルキル基である。
上記炭化水素基は、置換基を有していてもよい。
ｘは１以上３０以下の整数、ｙは１以上５以下の整数、ｚは１以上１８以下の整数を示す。）

(In General Formula (II), A ′ is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ is a monovalent group, and R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group. Yes, R ⁸ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or a carbon atom number of 1 or more and 5 or less. It is an alkyl group.
The hydrocarbon group may have a substituent.
x represents an integer of 1 to 30, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. )

  The divalent linking group A ′ in the general formula (II) can be the same as A in the general formula (I). Among them, A ′ is preferably a divalent linking group containing a direct bond, a —CONH— group, or a —COO— group from the viewpoint of solubility in an organic solvent. From the viewpoint of heat resistance of the obtained polymer, solubility in propylene glycol monomethyl ether acetate (PGMEA) suitably used as a solvent, and a relatively inexpensive material, A ′ may be a —COO— group. preferable.

The hydrocarbon group for R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples include 2-ethylhexyl group, 2-ethoxyethyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that a double bond is present at the terminal of the alkenyl group.
Examples of the aliphatic hydrocarbon substituent such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent. The number of carbon atoms of the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less.
Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, Furthermore, you may have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 14 or less.
Examples of the substituent on the aromatic ring such as an aryl group and an aralkyl group include straight chain and branched alkyl groups having 1 to 4 carbon atoms, alkenyl groups, nitro groups, and halogen atoms.
The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In the above R ⁵ , x is an integer of 1 or more and 30 or less, preferably an integer of 1 or more and 26 or less, more preferably an integer of 1 or more and 18 or less, still more preferably 1 or more and 4 or less, particularly preferably 1 or more and 2 Y is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 4 or less, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably an integer of 1 or more and 4 or less, more preferably an integer of 1 or more and 2 or less.

The hydrocarbon group for R ⁸ can be the same as that shown for R ⁵ . Among these, the hydrocarbon group for R ⁸ is preferably an alkyl group having 1 to 18 carbon atoms from the viewpoint of excellent developability.
R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be linear, branched or cyclic.
Moreover, R ⁵ in the structural unit represented by the general formula (II) may be the same or different from each other.

The R ⁵ is preferably selected so as to be excellent in compatibility with a solvent described later. Specifically, for example, the solvent is generally used as a solvent for a colored resin composition for a color filter. In the case of using a commonly used solvent such as glycol ether acetate, ether or ester, a methyl group, an ethyl group, an isobutyl group, an n-butyl group, a 2-ethylhexyl group, a benzyl group or the like is preferable.
In the structural unit constituting the B block, as R ⁵ , — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z — It contains what is R ⁸ is, excellent developability, from the viewpoint of excellent suppression of development residue.

Furthermore, R ⁵ may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an epoxy group, or an isocyanate group as long as the dispersion performance of the block copolymer is not hindered. After the synthesis of the polymer, the substituent may be added by reacting with the compound having the substituent.

In the present invention, the glass transition temperature (Tg) of the solvent-compatible block part of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-compatible block part is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher.
The glass transition temperature (Tg) of the solvent-affinity block part in the present invention can be calculated by the following formula. Similarly, the glass transition temperature of the colorant affinity block portion and the block copolymer can be calculated.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the solvent-affinity block portion. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature value (Tgi) of each monomer may be the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EH Immergut (Wiley-Interscience, 1989)). it can.

  What is necessary is just to adjust suitably the number of the structural units which comprise a solvent affinity block part in the range which a color material dispersibility improves. Among them, the number of structural units constituting the solvent-affinity block part is 10 or more and 200 or less from the viewpoint that the solvent-affinity part and the colorant affinity part act effectively and improve the dispersibility of the colorant. Preferably, it is 10 or more and 100 or less, more preferably 10 or more and 70 or less.

  The solvent-affinity block part may be selected so as to function as a solvent-affinity site, and the repeating unit constituting the solvent-affinity block part may be composed of one kind, or two or more kinds. The repeating unit may be included.

In particular, in the present invention, the dispersant is a polymer having a structure represented by the general formula (II) and having an amine value of 40 mgKOH / g to 120 mgKOH / g. It is preferable from the viewpoint of improving luminance and contrast without depositing foreign matters.
When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and is also excellent in alkali developability and solvent resolubility. In the present invention, the amine value of the dispersant is preferably 60 mgKOH / g or more, more preferably 90 mgKOH / g or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 115 mgKOH / g or less, and more preferably 105 mgKOH / g or less.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of a sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if it is an amino group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant is itself The amine value of can be measured.

The acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more as a lower limit 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 of more excellent development residue suppression effect. On the other hand, the acid value of the dispersant may be less than 1 mgKOH / g, preferably 0 mgKOH / g, from the viewpoint of dispersibility and dispersion stability. In addition, the acid value of the dispersant used in the present invention is 18 mgKOH / g or less as the upper limit of the acid value of the dispersant from the viewpoint of preventing deterioration in development adhesion and solvent resolubility. preferable. Among these, the acid value of the dispersant is more preferably 12 mgKOH / g or less, and even more preferably 8 mgKOH / g or less, from the viewpoint that the development adhesion and the solvent re-solubility are improved.
In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1 mgKOH / g or more, and more preferably 2 mgKOH / g or more. This is because the effect of suppressing the development residue is improved. On the other hand, the acid value of the block copolymer before salt formation may be less than 1 mgKOH / g, preferably 0 mgKOH / g, from the viewpoint of dispersibility and dispersion stability. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 12 mgKOH / g or less, and even more preferably 8 mgKOH / g or less. . This is because the development adhesiveness and the solvent resolubility are improved.

Moreover, in this invention, it is preferable that the glass transition temperature of a dispersing agent is 30 degreeC or more from the point which image development adhesiveness improves. That is, whether the dispersant is a block copolymer before salt formation or a salt block copolymer, the glass transition temperature is preferably 30 ° C. or higher. When the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C.), and the development adhesion may be lowered. This is presumably because when the glass transition temperature is close to the developer temperature, the movement of the dispersant increases during development, resulting in poor development adhesion. When the glass transition temperature is 30 ° C. or higher, the molecular motion of the dispersant during development is suppressed, so that it is estimated that the decrease in development adhesion is suppressed.
The glass transition temperature of the dispersant is preferably 32 ° C. or higher, more preferably 35 ° C. or higher, from the viewpoint of development adhesion. On the other hand, the temperature is preferably 200 ° C. or lower from the viewpoint of operability during use, such as easy precision weighing.
The glass transition temperature of the dispersant in the present invention can be determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

  When the colorant concentration is increased and the dispersant content is increased, the amount of the binder is relatively decreased. Therefore, the colored resin layer is easily peeled off from the base substrate during development. When the dispersant contains a B block containing a structural unit derived from a carboxy group-containing monomer and has the specific acid value and glass transition temperature, the development adhesion is improved. If the acid value is too high, the developability is excellent, but it is presumed that the polarity is too high and peeling easily occurs during development.

  From the above, in the present invention, the dispersant is a polymer having a structure represented by the general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less, and an acid value. 1 mgKOH / g or more and 18 mgKOH / g or less and a glass transition temperature of 30 ° C. or more is excellent in colorant dispersion stability, improves contrast, and suppresses generation of development residue when a colored resin composition is obtained. However, it is preferable from the viewpoint of excellent solvent resolubility and high development adhesion.

  As the carboxy group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by the general formula (I) and contains an unsaturated double bond and a carboxy group can be used. Examples of such monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use acid anhydride group containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxy group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the block copolymer before salt formation, the content ratio of the structural unit derived from the carboxy group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the range of the specific acid value. Although it is not limited, it is preferable that it is 0.05 mass% or more and 4.5 mass% or less with respect to the total mass of all the structural units of a block copolymer, and is 0.07 mass% or more and 3.7 mass% or less. More preferably.
Since the content ratio of the structural unit derived from the carboxy group-containing monomer is not less than the lower limit value, the effect of suppressing the development residue is expressed, and since it is not more than the upper limit value, the development adhesiveness is deteriorated and the solvent resolubility is reduced. Deterioration can be prevented.
In addition, the structural unit derived from a carboxy group containing monomer should just become said specific acid value, may consist of 1 type, and may contain 2 or more types of structural units.

  Moreover, the monomer whose glass transition temperature (Tgi) of the homopolymer of the monomer is 10 ° C. or higher from the viewpoint that the glass transition temperature of the dispersant used in the present invention is a specific value or higher and development adhesion is improved. Is preferably 75% by mass or more, and more preferably 85% by mass or more in the B block.

  In the block copolymer, the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. In view of the dispersibility and dispersion stability of the coloring material, it is more preferably within the range of 0.1 to 1.0.

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 or more and 20000 or less, and preferably 2000 or more and 15000 or less, from the viewpoint of improving the colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000 or more and 12000 or less.
Here, the weight average molecular weight (Mw) is determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC). The macromonomer, salt-type block copolymer, and graft copolymer that are the raw materials for the block copolymer are also subjected to the above conditions.

  The manufacturing method of the said block copolymer is not specifically limited. Although a block copolymer can be produced by a known method, it is preferable to produce it by a living polymerization method. This is because chain transfer and deactivation are unlikely to occur, a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include a living anionic polymerization method such as a living radical polymerization method and a group transfer polymerization method, and a living cation polymerization method. A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, a block copolymer can be produced by first producing the A block and polymerizing the structural units constituting the B block into the A block. In the above production method, the order of polymerization of the A block and the B block can be reversed. Also, the A block and the B block can be manufactured separately, and then the A block and the B block can be coupled.

  Specific examples of the block copolymer having a block part containing the structural unit represented by the general formula (I) and a block part having a solvent affinity include, for example, those described in Japanese Patent No. 4911253 A block copolymer can be mentioned as a suitable thing.

In the present invention, from the viewpoint of the dispersibility and dispersion stability of the color material, at least a part of the amino groups in the polymer containing the structural unit represented by the general formula (I), an organic acid compound, It is also preferable to use a salt formed with a halogenated hydrocarbon as a dispersant (hereinafter, such a polymer may be referred to as a salt-type polymer).
Among them, the polymer containing a repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. And preferred from the viewpoint of excellent dispersion stability. Specific examples of the organic acid compound used for such a dispersant include organic acid compounds described in JP 2012-236882 A and the like.
The halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride and aralkyl halides from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

In the color material dispersion of the present invention, as the dispersant, at least one polymer having the structural unit represented by the general formula (I) is used, and the content thereof is the type of the color material to be used, and further described below. It is appropriately selected according to the solid content concentration in the colored resin composition for color filter to be performed.
The content of the dispersant is 3 parts by mass or more and 45 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass with respect to 100 parts by mass of the total solid content in the colorant dispersion from the viewpoint of dispersibility and dispersion stability. It is preferable to mix | blend in the ratio below a mass part.
In particular, when forming a coating film or a colored layer having a high color material concentration, the content of the dispersant is 3 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the total solid content in the color material dispersion. More preferably, it is blended at a ratio of 5 parts by mass or more and 20 parts by mass or less.
In the present invention, the solid content is everything except the above-mentioned solvent, and includes monomers dissolved in the solvent.

<Solvent>
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the colorant dispersion and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, i-propyl alcohol and methoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate and methoxypropion. Ester solvents such as methyl acid, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, n-butyl butyrate, clohexanol acetate; acetone, Ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoate Glycol ether acetate solvents such as -3-methyl-1-butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; carbitol acetates such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA) Solvents: diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol Ethyl methyl ether, propylene glycol monomer Glycol ether solvents such as ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; tetrahydrofuran and the like Cyclic ether solvents such as: unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; aromatic hydrocarbons such as toluene and xylene Organic solvents such as Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, as a solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, butyl carbitol acetate (BCA), 3-methoxy One or more selected from the group consisting of -3-methyl-1-butyl acetate, ethyl lactate, methyl 2-hydroxypropionate, and 3-methoxybutyl acetate, solubility of other components and coating It is preferable from the point of aptitude.

  Moreover, it is also preferable to use the mixed solvent containing 2 or more types of solvents from viewpoints, such as developability and solvent re-dissolution property.

  When a mixed solvent is used, the glycol ether acetate described above is used as the first solvent because of its high safety; moderate volatility; good dispersibility due to moderate solubility; It is preferable to use a system solvent. Among them, 2-methoxyethyl acetate or propylene glycol monomethyl ether acetate having a boiling point (boiling point at atmospheric pressure; hereinafter the same) is less than 150 ° C. is more preferable, and propylene glycol monomethyl ether acetate (PGMEA) is particularly preferable. preferable.

  As the second solvent (a solvent other than the first solvent), a solvent having an alcoholic hydroxyl group or a solvent having a boiling point of 150 ° C. or higher is preferable. A 2nd solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

When a solvent having an alcoholic hydroxyl group is used as the second solvent, the dispersibility is improved and the solvent resolubility is likely to be improved.
Examples of the solvent having an alcoholic hydroxyl group include the alcohol solvent, the carbitol solvent, and the glycol ether solvent. Specific examples include propylene glycol monomethyl ether (boiling point 121 ° C.), 3-methoxy- Examples include 3-methyl-1-butanol (boiling point 174 ° C.).

In the case of using a mixed solvent, the content of the solvent having an alcoholic hydroxyl group is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less in the total solvent. Moreover, 0.1 mass% or more is preferable, 0.3 mass% or more is more preferable, and 1 mass% or more is still more preferable.
Within the above range, the solubility of the dispersant tends to be good, and since the dissolution of the dispersant in the first solvent is not hindered, the dispersion stability tends to be good.

When the first solvent is a solvent having a boiling point of less than 150 ° C., if a solvent having a boiling point of 150 ° C. or more is used as the second solvent, drying unevenness is less likely to occur, foreign matter is less likely to occur, and solvent resolubility is likely to be good. .
Examples of solvents having a boiling point of 150 ° C. or higher include diethylene glycol ethyl methyl ether (boiling point 179 ° C.), 3-methoxy-3-methyl-1-butyl acetate (boiling point 188 ° C.), diethylene glycol ethyl methyl ether (boiling point 179 ° C.), 3 -Methoxybutyl acetate (boiling point 172 ° C.) and the like.

When using a mixed solvent, the content of the solvent having a boiling point of 150 ° C. or higher is preferably 40% by mass or less, more preferably 30% by mass or less in the total solvent. Moreover, 3 mass% or more is preferable, 5 mass% or more is more preferable, and 10 mass% or more is still more preferable.
Within the above range, drying unevenness is unlikely to occur, and the drying time does not become too long and the productivity tends to be good.

  The boiling point of the “solvent having a boiling point of 150 ° C. or higher” is preferably 240 ° C. or lower, particularly preferably 200 ° C. or lower, from the viewpoint that the drying time does not become too long.

  In the color material dispersion of the present invention, the solvent as described above is usually preferably in the range of 55% by mass to 95% by mass with respect to the total amount of the color material dispersion containing the solvent. It is preferably in the range of not less than mass% and not more than 90 mass%, more preferably in the range of not less than 70 mass% and not more than 88 mass%. Within the above range, dispersibility is improved, viscosity stability is obtained, and a target chromaticity coordinate can be achieved.

<Other ingredients>
As long as the effect of this invention is not impaired, you may mix | blend a dispersion auxiliary resin and another component with the coloring material dispersion liquid of this invention as needed.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by a colored resin composition for a color filter described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, which may have the effect of stabilizing the dispersion and reducing the dispersant due to the dispersion stabilizing effect.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

  The color material dispersion of the present invention is used as a preliminary preparation for preparing a colored resin composition for a color filter described later. That is, the color material dispersion is P / V (total color material mass in the composition) / (color material in the composition), which is preliminarily prepared in a stage before preparing a colored resin composition for a color filter described later. Is a colorant dispersion having a high ratio of the total solid content other than Specifically, the ratio of (total colorant mass in the composition) / (total solid content other than colorant in the composition) is usually 1.0 or more. By mixing the colorant dispersion and each component described below, a colored resin composition for color filters having excellent dispersibility can be prepared.

[Production method of colorant dispersion]
In the present invention, the method for producing the color material dispersion is not particularly limited as long as the color material is a method for obtaining a color material dispersion dispersed in a solvent with the dispersant. Especially, it is preferable to set it as either of the following two manufacturing methods from the point which is excellent in the dispersibility and dispersion stability of a coloring material.

  That is, the first method for producing a colorant dispersion according to the present invention includes a step of preparing the dispersant and a step of dispersing the colorant in the presence of the dispersant in a solvent. . Two or more kinds of color materials may be co-dispersed in the presence of the dispersant in a solvent, or one or more kinds of color materials are dispersed or co-dispersed, and then two or more kinds of color material dispersions are mixed. By doing so, the colorant dispersion of the present invention may be obtained.

  In addition, when a dispersant that is a salt type block copolymer is used, the second method for producing the colorant dispersion according to the present invention includes a solvent, the block copolymer, the organic acid compound, and halogenated carbonization. While mixing hydrogen and a coloring material, salt formation of at least a part of the terminal nitrogen moiety of the structural unit represented by the general formula (I) with the organic acid compound or the halogenated hydrocarbon is performed. And a step of dispersing the coloring material. Even when the color material is dispersed while forming such a salt, two or more kinds of color materials may be co-dispersed, or after one or more kinds of color materials are dispersed or co-dispersed, two or more kinds of colors are dispersed. The color material dispersion of the present invention may be obtained by mixing the material dispersion.

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

[Colored resin composition for color filter]
The colored resin composition for a color filter according to the present invention is a colored resin composition for a color filter containing a coloring material, a dispersant, a binder component, and a solvent,
The color material is a blue color material, a purple color material, and C.I. I. Including Pigment Green 59,
The dispersant is a polymer having a structural unit represented by the general formula (I).
The colored resin composition for a color filter of the present invention is excellent in color material dispersion stability like the color material dispersion of the present invention, and as described in the section of the color material dispersion of the present invention, A colored layer having improved solubility and an expanded blue reproduction range can be formed.

  The colored resin composition for a color filter of the present invention contains at least a colorant, a dispersant, a binder component, and a solvent, and further contains other components as long as the effects of the present invention are not impaired. You may do it. Hereinafter, each component contained in the colored resin composition for a color filter of the present invention will be described. The blue color material, purple color material, PG59, dispersant, and solvent, which are essential components among the color materials, are described above. Since it is the same as that described in the color material dispersion of the invention, description thereof is omitted here.

<Color material>
The color material in the colored resin composition for a color filter of the present invention includes, as essential components, a blue color material, a purple color material, and C.I. I. Pigment Green 59 is included, but other color materials may be used in combination in order to adjust the color tone.
It is not particularly limited as long as it can form a desired color when forming the color layer of the color filter, and various organic pigments, inorganic pigments, dispersible dyes may be used alone or in combination of two or more. Can be used. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.
The dispersible dyes include dyes that are dispersible by imparting various substituents to the dyes or insolubilizing in a solvent by using a known lake (chlorination) technique, and low solubility. Examples thereof include dyes that are dispersible by using in combination with a solvent. By using such a dispersible dye in combination with the dispersant, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
As a guide, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

Among other color materials, other green color materials and red color materials are preferably used.
Examples of other color materials include, but are not limited to, the following.
As a red color material, C.I. I. Pigment Red 177, 168, 254, etc.
As a green color material, C.I. I. Pigment Green 7, 36, 58, etc.

In the colored resin composition for a color filter of the present invention, the content ratio of the blue color material to the entire color material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity.
Among them, it is preferable that the blue color material is contained in an amount of 15% by mass or more and 98% by mass or less based on the total amount of the color material from the viewpoint that the solvent re-solubility is improved and a colored layer having an expanded blue reproduction range can be formed. The blue color material is more preferably contained in an amount of 20% by mass or more and 90% by mass or less, still more preferably 25% by mass or more and 80% by mass or less, and particularly preferably 27% by mass or more and 70% by mass or less. .

In the photosensitive colored resin composition for color filters of the present invention, the content ratio of the purple color material to the blue color material may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the point that the solvent re-solubility is improved and a colored layer with an expanded blue reproduction range can be formed, the blue color material is contained in an amount of 3 parts by mass to 100 parts by mass with respect to 100 parts by mass. It is preferable to contain 5 parts by weight or more and 80 parts by weight or less.
The purple color material is preferably contained in an amount of 1% by mass to 45% by mass, more preferably 3% by mass to 40% by mass, and more preferably 5% by mass to 40% by mass with respect to the total amount of the color material. It is more preferable to contain, and it is still more preferable to contain 10 to 40 mass%.

In the photosensitive colored resin composition for color filters of the present invention, the content ratio of PG59 with respect to the blue color material is not particularly limited as long as it is appropriately adjusted according to the desired chromaticity. Among them, from the point that the solvent re-solubility is improved and a colored layer with an expanded blue reproduction range can be formed, the blue colorant is contained in an amount of 2 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass. It is preferable to contain 5 parts by mass or more and 200 parts by mass or less.
Moreover, it is preferable to contain PG59 1 mass% or more and 65 mass% or less with respect to coloring material whole quantity, It is more preferable to contain 2 mass% or more and 60 mass% or less, It contains 10 mass% or more and 50 mass% or less. It is even more preferable.

  In the photosensitive colored resin composition for a color filter of the present invention, the content ratio of the purple color material relative to PG59 may be appropriately adjusted according to the desired chromaticity, and is not particularly limited. Among them, from the point that a solvent re-solubility is improved and a colored layer with an expanded blue reproduction range can be formed, PG59 is contained in an amount of 0.03 parts by mass to 20 parts by mass with respect to 1 part by mass. It is preferable to contain 0.05 mass part or more and 10 mass parts or less, and it is still more preferable to contain 0.1 mass part or more and 7 mass parts or less.

  From the viewpoint of improving the solvent re-solubility and forming a colored layer with an expanded blue reproduction range, the blue color material is 15% by mass or more and 98% by mass with respect to the total amount of the color material as a suitable mixing ratio or combination. Hereinafter, the purple color material is preferably 1% by mass to 45% by mass, PG59 is preferably 1% by mass to 65% by mass, the blue color material is 20% by mass to 90% by mass, and the purple color material is 1% by mass. % To 45% by mass, PG59 is more preferably 1% to 65% by mass, blue color material is 25% to 80% by mass, purple color material is 3% to 40% by mass, More preferably, PG59 is 2 mass% or more and 60 mass% or less, blue color material is 27 mass% or more and 70 mass% or less, purple color material is 10 mass% or more and 40 mass% or less, and PG59 is 10 mass% or more. 50% by mass or less Theft is particularly preferred.

Moreover, in the photosensitive coloring resin composition for color filters of this invention, when it contains further green color materials other than PG59, the content rate of the green color material containing PG59 with respect to the whole color material is match | combined with desired chromaticity. It may be adjusted as appropriate and is not particularly limited.
Even in the case of further containing a green color material other than PG59, PG59 is preferably more than 50% by mass, more preferably 70% by mass or more based on the total amount of the green color material including PG59. It is more preferable that it is 80 mass% or more.
The content ratio of the green color material including PG59 with respect to the entire color material, the content ratio of the purple color material with respect to the green color material including PG59 are the content ratio of PG59 with respect to the entire color material, and the content ratio of the purple color material with respect to PG59, respectively. It is preferable that it is the same.

  Further, in the photosensitive colored resin composition for a color filter of the present invention, among them, the yellow color material is 0.1% by mass or less with respect to the total amount of the color material because a colored layer with an expanded blue reproduction range can be formed. It is preferable that it is less than 0.01% by mass.

  Moreover, in the photosensitive coloring resin composition for color filters of this invention, in the range which does not impair the effect of this invention, other color materials other than a blue color material, a purple color material, and PG59 are further included in a color material. The total content of the blue color material, the purple color material, and PG59 is more preferably 70% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass with respect to the total color material. % Or less is even more preferable.

<Binder component>
The colored resin composition for a color filter of the present invention contains a binder component in order to impart film formability and adhesion to the surface to be coated. In order to impart sufficient hardness to the coating film, it is preferable to contain a curable binder component. It does not specifically limit as a curable binder component, The curable binder component used in forming the coloring layer of a conventionally well-known color filter can be used suitably.
Examples of the curable binder component include a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. What contains the thermosetting binder component to contain can be used.

When using a photolithography process when forming a colored layer, the photosensitive binder component which has alkali developability is used suitably. In addition, you may further use a thermosetting binder component for the photosensitive binder component.
Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include a system containing an alkali-soluble resin and an o-quinonediazide group-containing compound as a photosensitizing component.

On the other hand, as the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used.
In the colored resin composition for a color filter according to the present invention, a negative photosensitive binder component is preferable because a pattern can be easily formed by an existing process by a photolithography method.

In order to expand the blue reproduction range, as described in Patent Document 1, a blue color material and a green color material such as PG58, PG7, or PG36 are combined with a negative photosensitive binder component to produce a photosensitive material for a blue colored layer. When the photosensitive colored resin composition is used, the photosensitive colored resin composition absorbs around 300 nm, which is the absorption wavelength (radical generation wavelength) of the photoinitiator, so that insufficient curing inside the colored layer occurs during exposure. , Chipping at the time of development, and accompanying development, chipping and peeling easily occur. Further, when voids (spaces inside the colored layer) are generated due to solidification only on the surface, the color unevenness due to irregular reflection of light when the colored layer is viewed from an oblique direction occurs. Also, if the colored layer has a gap, the application of the next colored layer, overcoat layer, etc. causes the resin composition to flow into the gap and the coating liquid is interrupted, causing uneven coating. there were.
On the other hand, in the present invention, the two types of purple color material and PG59 are mixed with the blue color material, so that the combination of the two types of purple color material and PG59 hardly absorbs the wavelength around 300 nm. Even when a photosensitive binder component is combined with a photosensitive colored resin composition for a blue colored layer, there is an advantage that insufficient curing inside the colored layer hardly occurs during exposure. Therefore, when the colored resin composition of the present invention is used as a photosensitive colored resin composition for a blue colored layer, it is difficult to cause chipping or peeling during development, as well as voids during development. There is an effect that color unevenness due to irregular reflection of light when the colored layer is viewed from an oblique direction hardly occurs.

  Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator constituting the negative photosensitive binder component will be specifically described.

(Alkali-soluble resin)
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
In the present invention, the alkali-soluble resin can be based on an acid value of 40 mgKOH / g or more.
A preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. Specifically, acrylic resins such as an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group are used. And epoxy (meth) acrylate resins having a carboxy group. Among these, particularly preferred are those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Moreover, acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination of two or more.

Acrylic resins such as an acrylic copolymer having a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group include, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co) polymer obtained by (co) polymerizing other polymerizable monomers by a known method.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. It is done. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring that is a bulky group in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is eased, and substrate adhesion is improved. Further, the present inventors have found that the use of an alkali-soluble resin having a hydrocarbon ring suppresses the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer. Although the action is unclear, the bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in an increase in the strength of the coating and suppression of swelling by the solvent. It is estimated that.
Examples of such hydrocarbon rings include aliphatic hydrocarbon rings that may have a substituent, aromatic hydrocarbon rings that may have a substituent, and combinations thereof. May have a substituent such as an alkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, or a halogen atom.
The hydrocarbon ring may be contained as a monovalent group or a divalent or higher group.

  Specific examples of the hydrocarbon ring include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0 (2,6)] decane (dicyclopentane), and adamantane. Rings: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, cardo structures (9,9-diarylfluorene), etc. Is mentioned.

When an aliphatic hydrocarbon ring is included as the hydrocarbon ring, it is preferable from the viewpoint of improving the heat resistance and adhesion of the colored layer and improving the luminance of the obtained colored layer.
Moreover, when the said cardo structure is included, the sclerosis | hardenability of a colored layer improves and it is especially preferable from the point which improves solvent resistance (NMP swelling suppression).

The alkali-soluble resin preferably has a bridged cyclic hydrocarbon ring, which is an aliphatic hydrocarbon ring having a structure in which two or more rings share two or more atoms.
Specific examples of the bridged cyclic hydrocarbon ring include norbornane, isobornane, adamantane, tricyclo [5.2.1.0 (2,6)] decane, tricyclo [5.2.1.0 (2,6)]. Decene, tricyclopentene, tricyclopentane, tricyclopentadiene, dicyclopentadiene; groups in which a part of these groups are substituted with a substituent are mentioned.
Examples of the substituent include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a halogen atom.

  The lower limit of the number of carbon atoms in the crosslinked cyclic hydrocarbon ring is preferably 5 or more, and particularly preferably 7 or more, from the viewpoint of compatibility with other materials and solubility in an alkaline developer. The upper limit is preferably 12 or less, and particularly preferably 10 or less.

  The alkali-soluble resin preferably has a maleimide structure represented by the following general formula (III).

［一般式（ＩＩＩ）において、Ｒ^Ｍは、置換されていてもよい炭化水素環である。］

[In General Formula (III), R ^M represents an optionally substituted hydrocarbon ring. ]

  When the alkali-soluble resin has a maleimide structure represented by the general formula (III), it has a nitrogen atom in the hydrocarbon ring, and therefore is a basic polymer that has a structural unit represented by the general formula (I). The compatibility with the dispersant is very good, the development speed is high, and the effect of suppressing development residue is improved.

In R ^M of the general formula (III), specific examples of the optionally substituted hydrocarbon ring, those similar to the specific example of the hydrocarbon ring.
For example, aliphatic hydrocarbon rings such as cyclopentyl group, cyclohexyl group, cyclooctyl group, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, methoxyphenyl group, benzyl group, hydroxyphenyl group, An aromatic hydrocarbon ring such as a naphthyl group, and a group in which a part of these groups is substituted with a substituent are exemplified.

In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each constituent unit by using an acrylic copolymer having a constituent unit having a hydrocarbon ring separately from the constituent unit having a carboxy group. This is preferable because the amount of the structural unit having a hydrocarbon ring is increased to easily improve the function of the structural unit.
The acrylic copolymer having a structural unit having a carboxy group and the hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned “other monomer capable of copolymerization”. be able to.

  Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl. (Meth) acrylate, styrene, etc. are mentioned. From the point that the cross-sectional shape of the colored layer after development has a large effect of being maintained in the heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl ( It is preferable to use at least one selected from (meth) acrylate, benzyl (meth) acrylate, and styrene.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer can form a cross-linked bond in the curing step of the resin composition at the time of producing the color filter. The film strength of the cured film is further improved and the development resistance is improved, and the thermal contraction of the cured film is suppressed and the adhesiveness with the substrate is excellent.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxyl group of the alkali-soluble resin Or by introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain. Etc.

  The alkali-soluble resin of the present invention may further contain other structural units such as a structural unit having an ester group such as methyl (meth) acrylate and ethyl (meth) acrylate. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the colored resin composition for a color filter, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

  The alkali-soluble resin in the present invention is preferably an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, It is an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenic double bond. Is more preferable.

  The alkali-soluble resin can be made into an alkali-soluble resin having desired performance by appropriately adjusting the charged amount of each structural unit.

The charged amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more and more preferably 10% by mass or more with respect to the total amount of the monomer from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of suppressing film roughness on the pattern surface after development, the amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, and 40% by mass or less with respect to the total amount of monomers. More preferably.
When the proportion of the carboxyl group-containing ethylenically unsaturated monomer is equal to or higher than the lower limit, the coating film obtained has sufficient solubility in an alkaline developer, and the proportion of the carboxyl group-containing ethylenically unsaturated monomer is the upper limit. When it is below, there is a tendency that the formed pattern is not easily detached from the substrate and the pattern surface is not easily roughened during development with an alkali developer.

  In addition, in an acrylic resin such as an acrylic copolymer having a structural unit having an ethylenic double bond and a styrene-acrylic copolymer, which is more preferably used as an alkali-soluble resin, an epoxy group and an ethylenic double bond are used. The amount of the compound having a bond is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass or less with respect to the charged amount of the carboxyl group-containing ethylenically unsaturated monomer.

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

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxy group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones. The epoxy (meth) acrylate resin having a carboxy group may be used alone or in combination of two or more.

The alkali-soluble resin is preferably selected from those having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) with respect to an alkaline aqueous solution used for the developer. The alkali-soluble resin preferably has an acid value of 70 mgKOH / g or more and 300 mgKOH / g or less from the viewpoint of developability (solubility) with respect to an aqueous alkali solution used for the developer and adhesion to the substrate. It is preferable that it is 80 mgKOH / g or more and 280 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K 0070.

The ethylenically unsaturated bond equivalent in the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group improves the film strength of the cured film, improves the development resistance, and obtains the effect of excellent adhesion to the substrate. From the viewpoint, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes.
Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

Formula (1)
Ethylenically unsaturated bond equivalent (g / mol) = W (g) / M (mol)
(In Formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

  The ethylenically unsaturated bond equivalent is determined, for example, by measuring the number of ethylenic double bonds contained in 1 g of alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992. It may be calculated.

  The alkali-soluble resin used in the colored resin composition for color filters may be used alone or in combination of two or more, and the content is not particularly limited, but for color filters. The alkali-soluble resin is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less, based on the total solid content of the colored resin composition. When the content of the alkali-soluble resin is not less than the above lower limit, sufficient alkali developability can be easily obtained, and when the content of the alkali-soluble resin is not more than the above upper limit, film roughness or lack of pattern can be caused during development. It is easy to suppress.

(Polyfunctional monomer)
The polyfunctional monomer used in the colored resin composition for a color filter is not particularly limited as long as it can be polymerized by the photoinitiator, and usually a compound having two or more ethylenically unsaturated double bonds. A polyfunctional (meth) acrylate is preferably used, and particularly has two or more acryloyl groups or methacryloyl groups.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include those described in JP2013-029832A.

  These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, when the photocurability (high sensitivity) is requested | required of the colored resin composition for color filters of this invention, a polyfunctional monomer has three (trifunctional) or more of the double bond which can superpose | polymerize. Preferred are poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid modified products. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, modified succinic acid of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate Dipentaeri modified from succinic acid Ritoruhekisa (meth) acrylate are preferable.

  Although there is no restriction | limiting in particular in content of the said polyfunctional monomer used in the colored resin composition for color filters, Preferably a polyfunctional monomer is 5 mass% or more and 60 with respect to the solid content whole quantity of the colored resin composition for color filters. It is within the range of 10% by mass or less and more preferably 40% by mass or less. When the content of the polyfunctional monomer is not less than the above lower limit, photocuring proceeds sufficiently, and the exposed portion can suppress elution during development, and when the content of the polyfunctional monomer is not more than the above upper limit, alkali development Sex is enough.

(Photoinitiator)
There is no restriction | limiting in particular as an initiator used in the colored resin composition for color filters of this invention, From the conventionally known various initiators, it can be used 1 type or in combination of 2 or more types.
Examples of the initiator include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-amino ketones, biimidazoles, N, N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, thioxanthone, and the like. Can do. Specific examples of the initiator include aromatic ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzoin ethers such as benzoin methyl ether, and benzoin such as ethylbenzoin. , Biimidazoles such as 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, and halo such as 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Methyloxadiazole compounds, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 Morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4 -Benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone 2,4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- 4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1- For example, propanone.
Among them, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1- Butanone, 4,4′-bis (diethylamino) benzophenone, and diethylthioxanthone are preferably used. Furthermore, a combination of an α-aminoacetophenone initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and a thioxanthone initiator such as diethylthioxanthone is sensitive. It is preferable from the viewpoint of suppressing adjustment and water stain and improving development resistance.
The total content of the α-aminoacetophenone initiator and the thioxanthone initiator is preferably 5% by mass or more and 15% by mass or less with respect to the total solid content of the colored resin composition. When the amount of the initiator is 15% by mass or less, sublimates during the production process are reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water stain is improved.

In the present invention, the initiator preferably contains an oxime ester photoinitiator from the viewpoint of improving sensitivity. By using an oxime ester photoinitiator, in-plane line width variations are easily suppressed when forming a fine line pattern. Furthermore, by using an oxime ester photoinitiator, the development resistance is improved, and the effect of suppressing the occurrence of water stain tends to be increased. In addition, water stain means that, when a component that enhances alkali developability is used, a trace of water stain is generated after rinsing with pure water after alkali development. Such water stain disappears after post-baking, so there is no problem as a product, but it is detected as unevenness in the appearance inspection of the patterning surface after development, and there is a problem that it is impossible to distinguish between normal products and abnormal products. Arise. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which becomes a problem.
As the oxime ester photoinitiator, those having an aromatic ring are preferable from the viewpoint of reducing contamination of the colored resin composition for a color filter by a decomposition product and contamination of the apparatus, and having a condensed ring including an aromatic ring. More preferred are those having a condensed ring containing a benzene ring and a heterocycle.
As the oxime ester photoinitiator, 1,2-octadion-1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), JP 2000-80068 A, JP 2001-233842 A, Special Table 2010-527339, Special Table 2010-527338, It can be appropriately selected from oxime ester photoinitiators described in JP2013-041153A and the like. As commercially available products, Irgacure OXE-02 (manufactured by BASF) having a carbazole skeleton, Adeka Arcles NCI-831 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials), ADEKA having a diphenyl sulfide skeleton Arcles NCI-930 (manufactured by ADEKA), TR-PBG-345, TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials), Irgacure OXE-01 (manufactured by BASF), TR-PBG having a fluorene skeleton -365 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.) or the like may be used. In particular, it is preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of luminance. It is preferable to use an oxime ester photoinitiator having a carbazole skeleton from the viewpoint of high sensitivity.
Moreover, it is preferable to use two or more kinds of oxime ester photoinitiators in terms of easily improving development resistance and luminance, and having a high effect of suppressing the occurrence of water stain. In particular, the combined use of two types of oxime ester photoinitiators having a diphenyl sulfide skeleton, or the combined use of an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having a fluorene skeleton is high in luminance and heat resistance. It is preferable from the point of high property. In addition, the combined use of an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having a fluorene skeleton or an oxime ester photoinitiator having diphenyl sulfide is excellent in sensitivity and water stain generation suppression effect. Is preferable.

In addition, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester photoinitiator from the viewpoint of suppressing water stain and improving sensitivity. Since the photoinitiator having a tertiary amine structure has a tertiary amine structure that is an oxygen quencher in the molecule, radicals generated from the initiator are hardly deactivated by oxygen, and sensitivity can be improved. is there. As a commercial item of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 4,4′-bis (diethylamino) benzophenone (for example, High Cure ABP, Kawaguchi Pharmaceutical).
In addition, combining an oxime ester photoinitiator with a thioxanthone initiator is preferable from the viewpoint of adjusting sensitivity, suppressing water stain, and improving development resistance. Two or more oxime ester photoinitiators and a thioxanthone photoinitiator are preferable. A combination of initiators is preferable in that brightness and development resistance are improved, sensitivity adjustment is easy, water stain generation suppression effect is high, and development resistance is improved.

The content of the photoinitiator used in the colored resin composition for a color filter of the present invention is usually about 0.01 parts by mass or more and 100 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. The amount is 60 parts by mass or less. If this content is not less than the above lower limit, the photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development, while if it is not more than the above upper limit, the yellowing of the resulting colored layer is weakened and the luminance is reduced. It can suppress that it falls.
Moreover, as a photoinitiator used in the colored resin composition for color filters of the present invention, the total content of two or more oxime ester photoinitiators is based on the total solid content of the colored resin composition for color filters. 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less in the range of sufficiently exhibiting the combined effect of these photoinitiators. To preferred.

  The binder component used in the colored resin composition for a color filter of the present invention preferably has a total content of 35% by mass to 97% by mass with respect to the total solid content of the colored resin composition for a color filter. It is more preferable to blend in a proportion of not less than mass% and not more than 96 mass%. If it is more than the said lower limit, the colored layer excellent in hardness and the adhesiveness with a board | substrate can be obtained. Moreover, if it is below the said upper limit, it is excellent in developability and generation | occurrence | production of the fine wrinkles by heat shrink is also suppressed.

<Optional components>
The colored resin composition for a color filter may contain various additives as necessary.
Examples of additives include, in addition to antioxidants, mercapto compounds, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters. Etc.

It is preferable that the colored resin composition for a color filter of the present invention further contains an antioxidant because heat resistance is improved, fading of the coloring material is suppressed, and luminance is improved.
The antioxidant may be appropriately selected from conventionally known antioxidants. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. From the viewpoint, it is preferable to use a hindered phenol-based antioxidant.

The hindered phenol antioxidant contains at least one phenol structure, and has a structure in which a substituent having 4 or more carbon atoms is substituted on at least one of the 2-position and 6-position of the hydroxyl group of the phenol structure. Means an antioxidant.
Specific examples of the hindered phenol antioxidant include, for example, dibutylhydroxytoluene (BHT), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by BASF), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6 -Tris (4-hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 6- (4-hydroxy-3,5-di-tert-butylanilino) -2 , 4-Bis (octylthio) -1,3,5-triazine (trade name: Irganox 565) BASF), 2,2′-thiodiethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1035, manufactured by BASF), 1,2-bis [3- (4-hydroxy-3,5-di-tert-butylphenyl) propionyl] hydrazine (trade name: Irganox MD1024, manufactured by BASF), 3- (4-hydroxy-3,5-diisopropylphenyl) propionic acid Octyl (trade name: Irganox 1135, manufactured by BASF), 4,6-bis (octylthiomethyl) -o-cresol (trade name: Irganox 1520L, manufactured by BASF), N, N′-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide] (trade name: Irganox) 1098, manufactured by BASF), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 259, manufactured by BASF), 1-dimethyl- 2-[(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: ADK STAB AO-80 , Manufactured by Adeka), bis (3-tert-butyl-4-hydroxy-5-methylbenzenepropionic acid) ethylene bis (oxyethylene) (trade name: Irganox 245, manufactured by BASF), 1,3,5-tris [ [4- (1,1-dimethylethyl) -3-hydroxy-2,6-dimethylphenyl] methyl] -1,3,5-triazine- , 4,6 (1H, 3H, 5H) -trione (trade name: Irganox 1790, manufactured by BASF), 2,2′-methylenebis (6-tert-butyl-4-methylphenol) (trade name: Sumilyzer MDP- S, manufactured by Sumitomo Chemical Co., Ltd.), 6,6′-thiobis (2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxy Diethyl benzylphosphonate (trade name: Irgamod 195, manufactured by BASF), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate (trade name: Sumilizer GM, manufactured by Sumitomo Chemical Co., Ltd., 4,4'-thiobis (6-tert-butyl-m-cresol) (trade name: Sumilizer WX R, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-di -tert- butyl-4,4'-Buchiridenji -m- cresol (trade name: ADK STAB AO-40, manufactured by ADEKA), and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.
Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .
In addition, a hindered phenol antioxidant having a molecular weight of 1000 or less and a molecular weight per phenolic hydroxyl group of 280 equivalents or less, and further a molecular weight of 500 or less and a molecular weight per phenolic hydroxyl group of 200 equivalents or less. Is preferable because a colored layer with improved brightness and contrast can be formed. Such an antioxidant has high fluidity and many active points per weight, so that radical trapping suppresses color material aggregation due to rapid curing shrinkage during exposure and post-baking, It is presumed that the above effect is easily obtained due to suppression of yellowing. Examples of such an antioxidant include 6,6′-di-tert-butyl-4,4′-butylidene di-m-cresol (trade name: ADK STAB AO-40, manufactured by ADEKA).

In the present invention, it is preferable to use a latent antioxidant as the antioxidant because a colored layer with improved contrast can be formed. The use of a latent antioxidant increases the radical trapping effect, especially during post-baking, so it is estimated that the above effect is likely to be obtained due to the suppression of color material aggregation due to rapid curing shrinkage during post-baking. Is done. In the present invention, the latent antioxidant is a compound having a protecting group that can be removed by heating, and exhibiting an antioxidant function when the protecting group is eliminated. Among them, those that can be easily removed by protecting at 150 ° C. or higher are preferable. For example, the latent antioxidant as described in international publication 2014/021023 is mentioned.
Examples of the latent antioxidant suitably used in the present invention include latent hindered phenol antioxidants in which the phenolic hydroxyl group of the hindered phenol antioxidant is protected with a protecting group that can be removed by heating. . As latent hindered phenolic antioxidants, phenolic hydroxyl groups of hindered phenolic antioxidants, acid anhydrides, acid chlorides, Boc reagents, alkyl halide compounds, silyl chloride compounds, allyl ether compounds, etc. And the reaction product. As the latent hindered phenol antioxidant, a structure in which the hydrogen of the phenol group of the hindered phenol antioxidant is substituted with a carbamate protecting group such as a t-butoxycarbonyl group is preferably used. Examples include the following chemical formulas (a) to (c), but are not limited thereto.

  The method for producing the latent antioxidant is not particularly limited. For example, JP-A-57-111375, JP-A-3-1733843, JP-A-6-128195, JP-A-7-207771, JP-A-7-252191, Special Tables. Obtained by reacting a phenolic compound produced by the method described in each publication of 2004-501128 with an acid anhydride, acid chloride, Boc reagent, alkyl halide compound, silyl chloride compound, allyl ether compound, etc. Can do. Moreover, you may use a commercial item.

  The colored resin composition for a color filter according to the present invention contains, as a photosensitive colored resin composition, a combination of the oxime ester photoinitiator and an antioxidant in a synergistic effect, and the outer portion of the mask opening. Curing with weak light penetrating into the surface is suppressed, resulting in chipping during development, and subsequent development of chipping and peeling, and color unevenness due to irregular reflection of light when the colored layer is viewed from an oblique direction. Furthermore, it is preferable from the point of being difficult to generate.

  As content of antioxidant, it is preferable that antioxidant is 0.05 mass part or more and 10.00 mass part or less with respect to 100 mass parts of total solids in a colored resin composition, 0.10 It is more preferable that the amount is not less than 5.00 parts by mass. If it is more than the said lower limit, it is excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the colored resin composition of this invention can be made into a highly sensitive photosensitive resin composition.

  When the antioxidant is used in combination with the oxime ester photoinitiator, the content of the antioxidant is 1 part by mass of the antioxidant with respect to 100 parts by mass of the total amount of the oxime ester photoinitiator. The amount is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more preferably 5 parts by mass or more and 45 parts by mass or less. If it is in the said range, it is excellent in the effect of the said combination.

It is preferable that the colored resin composition for a color filter of the present invention further contains a mercapto compound from the viewpoint of improving the effect of suppressing the occurrence of water stain.
In addition, the colored resin composition for a color filter of the present invention contains a combination of the oxime ester photoinitiator and a mercapto compound as a photosensitive colored resin composition, which improves development resistance and generates water stains. This is preferable because the suppression effect is further improved, and when forming a fine line pattern, the linearity is further improved, and the ability to form the fine line pattern as designed for the mask line width is improved. In addition, when the oxime ester photoinitiator and the mercapto compound are contained in combination, a synergistic effect makes it more difficult to cause erosion during development, and accompanying development, chipping or peeling, and a colored layer is formed from an oblique direction. This is preferable from the viewpoint that color unevenness due to irregular reflection of light when viewed is further less likely to occur.
“Improved linearity” means that the end of the colored layer formed in the development step after applying the colored composition has few irregularities and is linear or substantially linear.

The mercapto compound can function as a chain transfer agent, and has the property of receiving radicals from slowly reacting radicals to accelerate the reaction and improve curability.
Examples of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, and 3-mercaptopropionic acid. Methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), Pentaeri Lithol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) and the like.
As the mercapto compound, one or a combination of two or more may be used. Among them, one or more selected from the group consisting of polyfunctional mercapto compounds having two or more mercapto groups in one molecule may be used. It is preferable from the viewpoint that the crosslink density is increased and the effect of suppressing water stain is improved.
In addition, a secondary mercapto compound having a secondary mercapto group in which the carbon atom to which the mercapto group is bonded is a secondary carbon atom is preferable from the viewpoint that even when stored for a long period of time, a good water stain suppression effect is easily maintained. Further, a polyfunctional secondary mercapto compound having two or more secondary mercapto groups in one molecule is more preferable.

  The content of the mercapto compound used in the colored resin composition for color filter is not particularly limited, but the mercapto compound is 0.2% by mass or more and 7% by mass with respect to the total solid content of the colored resin composition for color filter. % Or less, and more preferably in the range of 0.5% by mass or more and 5% by mass or less from the viewpoint of sufficiently exhibiting the above effects.

  Moreover, it is preferable that the colored resin composition for color filters of this invention contains a ultraviolet absorber further from the point which can form the colored layer with improved contrast. The effect of improving these characteristics is presumed to be due to suppression of color material aggregation due to rapid curing shrinkage in the exposure process. What is necessary is just to select an ultraviolet absorber suitably from a conventionally well-known thing. Specific examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, triazine compounds, and the like. Among them, it is preferable to use a benzotriazole-based compound from the viewpoint that a colored layer with improved contrast can be formed.

Examples of the benzotriazole compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, and octyl-3 [3- t-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-t-butyl-4-hydroxy-5- (5- Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3- t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2- Droxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H -Benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3 3-tetramethylbutyl) phenol and the like, but are not limited thereto.
Examples of commercially available products include “TINUVIN P”, “TINUVIN PS”, “TINUVIN 109”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 328”, “TINUVIN 329”, and “TINUVIN 384-2” manufactured by BASF. ”,“ TINUVIN 900 ”,“ TINUVIN 928 ”,“ TINUVIN 99-2 ”,“ TINUVIN 1130 ”, and the like.

  As the benzotriazole-based compound, a benzotriazole-based compound represented by the following general formula (IV) is preferable because a colored layer with improved contrast can be formed.

（一般式（ＩＶ）中、Ｒ^１１及びＲ^１２はそれぞれ独立して、水素原子又はフェニル基で置換されていても良い炭素数１〜２０のアルキル基、Ｘは、水素原子又は塩素原子を表す。）

(In the general formula (IV), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a phenyl group, and X represents a hydrogen atom or a chlorine atom. .)

In general formula (IV), among them, R ¹² is preferably a methyl group, a t-butyl group, a t-amyl group, a t-octyl group, or an α, α-dimethylbenzyl group, and R ¹¹ is a hydrogen atom. An atom, a t-butyl group, a t-amyl group, or an α, α-dimethylbenzyl group is preferable.

  Although there is no restriction | limiting in particular in content of the ultraviolet absorber used in the colored resin composition for color filters, an ultraviolet absorber is 0.05 mass part or more with respect to 100 mass parts of total solids in a colored resin composition. It is preferably 10.00 parts by mass or less, and more preferably 0.10 parts by mass or more and 5.00 parts by mass or less. If it is more than the said lower limit, it is excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the colored resin composition of this invention can be made into a highly sensitive photosensitive resin composition.

  The colored resin composition for a color filter of the present invention contains a combination of the oxime ester photoinitiator and an ultraviolet absorber as a colored resin composition, and has a synergistic effect. It is preferable in that it is less likely to cause chipping and peeling, and color unevenness due to irregular reflection of light when the colored layer is viewed from an oblique direction is further less likely to occur.

  When the ultraviolet absorber is used in combination with the oxime ester photoinitiator, the content of the ultraviolet absorber is 1 part by mass with respect to 100 parts by mass of the total amount of the oxime ester photoinitiator. The amount is preferably 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and still more preferably 5 parts by mass or more and 45 parts by mass or less. If it is in the said range, it is excellent in the effect of the said combination.

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

  Moreover, it is preferable that the coloring resin composition for color filters of this invention contains a silane coupling agent further from the point which the peeling prevention of a coating film improves. Examples of the silane coupling agent include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403, Examples thereof include KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone). Among these, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 having a methacryl group and an acrylic group are preferable from the viewpoint of adhesion of the SiN substrate.

  The content of the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the total solid content in the colored resin composition. More preferably, it is 1 part by mass or more and 5.0 parts by mass or less. If it is more than the said lower limit and below the said upper limit, it is excellent in the peeling suppression of a coating film.

<Combination ratio of each component in the colored resin composition for color filter>
The total content of the color material is 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less, based on the total solid content of the colored resin composition for color filters. Is preferred. If it is more than the said lower limit, the colored layer at the time of apply | coating the colored resin composition for color filters to predetermined | prescribed film thickness (usually 1.0 micrometer or more and 5.0 micrometers or less) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In the case of forming a colored layer having a particularly high color material concentration, the content of the color material is 15% by mass or more and 65% by mass or less, more preferably 25% by mass with respect to the total solid content of the color resin composition for color filters. It is preferable to mix | blend in the ratio of the mass% or more and 60 mass% or less.
Further, the content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the content of the dispersant is 1 with respect to the total solid content of the colored resin composition for a color filter. It can be used in the range of mass% to 40 mass%. Furthermore, it is preferable to mix | blend in the ratio of 2 mass% or more and 30 mass% or less with respect to the solid content whole quantity of the colored resin composition for color filters, and it is preferable to mix | blend especially in the ratio of 3 mass% or more and 25 mass% or less. . If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a color material, and is excellent in the storage stability of the colored resin composition for color filters. Moreover, if it is below the said upper limit, developability will become favorable. When a colored layer having a particularly high colorant concentration is formed, the content of the dispersing agent is 2% by mass or more and 25% by mass or less, more preferably 3%, based on the total solid content of the colored resin composition for color filters. It is preferable to mix in a proportion of not less than 20% by mass and not more than 20% by mass.
Moreover, what is necessary is just to set content of a solvent suitably in the range which can form a colored layer accurately. Usually, it is preferably in the range of 55% by mass to 95% by mass with respect to the total amount of the colored resin composition for a color filter containing the solvent, and in particular, in the range of 65% by mass to 88% by mass. More preferably. When the content of the solvent is within the above range, the coating property can be excellent.

When combined with a negative photosensitive binder component to form a photosensitive colored resin composition for a blue colored layer, the blue color material in the color material, purple color, from the point of suppressing blurring, peeling, and color unevenness during development The color material ratio of the color material and PG59 (mass ratio) is preferably a color material ratio that satisfies the following average transmittance.
A test color material dispersion is prepared so that a predetermined color material ratio is obtained using an appropriate dispersant and solvent, and the test color material dispersion is prepared so that the total content of color materials is 0.001% by mass. Dilute with PGMEA, put the diluted test color material dispersion in a quartz cell with an optical path length of 10 mm, and perform spectral transmittance measurement. In the spectral transmittance measurement, the average transmittance in the range of 280 nm to 360 nm is preferably 36% or more, more preferably 39% or more, and still more preferably 40% or more. The spectral transmittance can be measured using an ultraviolet-visible spectrophotometer (for example, an ultraviolet-visible near-infrared spectrophotometer UV-3150 manufactured by Shimadzu Corporation).
Further, as the appropriate dispersant and solvent, specifically, for example, the dispersant and solvent used in the color material dispersion liquid of Example 1 described later can be used. It can be prepared in the same manner as the colorant dispersion of Example 1.

In addition, when a negative photosensitive binder component is combined to form a photosensitive colored resin composition for a blue colored layer, the blue color material in the color material is suppressed in terms of suppressing blurring, peeling, and color unevenness during development. The color material ratio (mass ratio) of the purple color material and PG59 is preferably a color material ratio that satisfies the following average transmittance.
In a chromaticity coordinate in the XYZ color system of JIS Z8701 measured by a C light source with a single pixel, the film thickness is 2.8 μm or less, x = 0.120 or more and 0.147 or less, y = 0. Cured film capable of displaying a color space in the range of 038 to 0.180, preferably a cured film capable of displaying a color space in the range of x = 0.125 to 0.147, y = 0.038 to 0.120 The color material ratio of the blue color material, purple color material, and PG59 in the color material is maintained, and 1 / 60,000 of the color material concentration of the cured film (total mass of the color material / total mass of the solid content of the cured film). A diluted test color material dispersion having a color material concentration (total color material mass / total color material dispersion containing solvent) is prepared, and the diluted test color material dispersion is placed in a quartz cell having an optical path length of 10 mm and spectrally transmitted. Take rate measurements. In the spectral transmittance measurement, the average transmittance in the range of 280 nm to 360 nm is preferably 42% or more, more preferably 44% or more, and even more preferably 46% or more. The spectral transmittance can be measured using an ultraviolet-visible spectrophotometer as described above.
In addition, the dilution test color material dispersion specifically includes, for example, a blue color material, a purple color material, and PG59 at a desired ratio based on the color material ratio in the cured film, and the color of Example 1 described later. A colorant dispersion was prepared in the same manner as in Example 1 using the dispersant and solvent used in the material dispersion, and the colorant concentration of the cured film (total mass of the colorant / total mass of the solid content of the cured film) was 6. It can be prepared by diluting with a solvent such as PGMEA so that the colorant concentration is 1 / 10,000 (total colorant mass / total colorant dispersion containing solvent).

  In the colored resin composition for a color filter of the present invention, the P / V ratio ((total color material mass) / (total solid content other than color material in the composition) ratio) is a blue reproduction range. Is preferably 0.10 or more, more preferably 0.15 or more, and still more preferably 0.20 or more. On the other hand, solvent resolubility, development residue, development From the viewpoint of excellent adhesion, development resistance, development chipping and unevenness generation suppression effect, contrast and the like, it is preferably 0.60 or less, more preferably 0.50 or less, and 0.45 or less. Is still more preferable, and it is especially preferable that it is 0.35 or less.

<Curing film of colored resin composition for color filter>
The colored resin composition for a color filter has chromaticity coordinates in an XYZ color system of JIS Z8701 measured using a C light source, where x = 0.110 to 0.150, y = 0.035 to 0.00. It is preferable that a cured film in the range of 190 or less can be formed.
Among these, chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source are x = 0.120 or more and 0.147 or less, y = 0.038 or more from the viewpoint of improving color reproducibility. It is preferable that a cured film in the range of 0.180 or less can be formed, and a cured film in the range of x = 0.122 to 0.147, y = 0.038 to 0.150 can be formed. More preferably, it is more preferable that a cured film in the range of x = 0.125 to 0.147 and y = 0.038 to 0.120 can be formed.

The cured film of the colored resin composition for a color filter has a thickness of 2.8 μm or less, and in the chromaticity coordinates in the XYZ color system of JIS Z8701 measured with a C light source with a single pixel, x = 0.120 or more and 0.147 or less, and y = 0.038 or more and 0.180 or less are preferably displayed. X = 0.122 or more and 0.147 or less, y = 0.038 or more and 0.0. It is more preferable that a color space in the range of 150 or less can be displayed, and it is even more preferable that a color space in the range of x = 0.125 to 0.147 and y = 0.038 to 0.120 can be displayed.
The cured film of the colored resin composition for a color filter has a thickness of 2.8 μm or less, and in the chromaticity coordinates in the XYZ color system of JIS Z8701 measured with a C light source with a single pixel, x = 0.137 or more and 0.147 or less, and y = 0.038 or more and less than 0.060, as a favorable blending ratio or combination, the blue color material is 43 with respect to the total amount of the color material. It is preferable that they are 14 mass% or more and 40 mass% or less, and PG59 is 1 mass% or more and 24 mass% or less.
Similarly, a good blending ratio or combination for displaying a color space in the range of x = 0.132 to 0.145 and y = 0.060 to less than 0.080 is a blue color with respect to the total amount of the color material. The color material is 43% by mass to 93% by mass, more preferably 43% by mass to 90% by mass, the purple color material is 5% by mass to 39% by mass, and PG59 is 1% by mass to 30% by mass. Is preferred.
Similarly, a good blending ratio or combination for displaying a color space in the range of x = 0.128 or more and 0.138 or less and y = 0.080 or more and less than 0.100 is blue with respect to the total amount of the color material. The color material is 35% by mass to 98% by mass, more preferably 35% by mass to 90% by mass, the purple color material is 1% by mass to 23% by mass, and PG59 is 1% by mass to 49% by mass. Is preferred.
Similarly, a good blending ratio or combination for displaying a color space in the range of x = 0.125 or more and 0.147 or less and y = 0.100 or more and less than 0.120 is blue with respect to the total amount of the color material. The color material is 25% by mass or more and 98% by mass or less, more preferably 27% by mass or more and 90% by mass or less, the purple color material is 1% by mass or more and 26% by mass or less, and PG59 is 1% by mass or more and 53% by mass or less. Is preferred.
Similarly, a good blending ratio or combination for displaying a color space in the range of x = 0.122 to 0.147 and y = 0.120 to less than 0.150 is blue with respect to the total amount of the color material. The color material is preferably 27% by mass or more and 89% by mass or less, the purple color material is 1% by mass or more and 26% by mass or less, and PG59 is preferably 10% by mass or more and 60% by mass or less.
Similarly, a good blending ratio or combination for displaying a color space in the range of x = 0.120 to 0.147 and y = 0.150 to 0.180 is blue with respect to the total amount of the color material. The color material is preferably 26% by mass to 73% by mass, the purple color material is preferably 1% by mass to 13% by mass, and PG59 is preferably 21% by mass to 65% by mass.
In addition, the film thickness of the cured film here is a film after applying the colored resin composition for color filter, drying, exposing to cure the polyfunctional monomer, and then post-baking in a clean oven at 230 ° C. for 30 minutes. Thickness.

<Method for producing colored resin composition for color filter>
The method for producing the colored resin composition for a color filter of the present invention is not particularly limited. For example, the color material dispersion of the present invention includes an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and as necessary. It can be obtained by adding other components and mixing them using a known mixing means. Alternatively, using the dispersant, each color material dispersion liquid is prepared, and each color material dispersion liquid, a binder component, and other components as necessary, using a known mixing means. It can be obtained by mixing.

[Color filter]
The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is a colored resin composition for a color filter according to the present invention. It has a colored layer which is a cured product.

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

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a cured product of the colored resin composition for a color filter according to the present invention, that is, a colored layer formed by curing the colored resin composition. .
The colored layer is usually formed in an opening of a light shielding part on the substrate to be 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 for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the colored resin composition for a color filter, but is usually preferably in the range of 1 μm to 5 μm.

The colored layer can be formed by the following method, for example.
First, the above-described colored resin composition for a color filter of the present invention is applied onto a substrate described later using a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. Apply to form a wet coating. Of these, spin coating and die coating can be preferably used.
Next, after drying the wet coating film using a hot plate or an oven, it is exposed through a mask having a predetermined pattern and cured by photopolymerization of an alkali-soluble resin and a polyfunctional monomer. Let it be a coating film. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition for the color filter to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition for color filters is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on 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 substrate to be described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light shielding part may be a metal thin film such as chromium by sputtering, vacuum deposition or the like. Alternatively, the light shielding part may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring the photosensitive resist, etc. is there.

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

(substrate)
As the substrate, a transparent substrate or a silicon substrate, which will be described later, or an aluminum, silver, or silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor such as a TFT, a circuit, or the like may be formed.

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing about 100 micrometers or more and 1 mm or less can be used, for example.
The color filter of the present invention includes, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, etc., in addition to the substrate, the light shielding portion, and the colored layer. Also good.

[Display device]
The display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device and an organic light emitting display device. In the present invention, even in a horizontal electric field type liquid crystal display device, various display defects such as liquid crystal orientation disorder due to the electrical characteristics of the green pixel and image sticking phenomenon due to switching threshold deviation are suppressed. The device is preferably selected.

<Liquid crystal display device>
The liquid crystal display device of the present invention includes the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram illustrating an example of a display device of the present invention, and is a schematic diagram illustrating an example of a liquid crystal display device. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

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

<Organic light-emitting display device>
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram illustrating another example of the display device of the present invention, and is a schematic diagram illustrating an example of an organic light emitting display device. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
In addition, the acid value of the block copolymer before salt formation was calculated | required by the method according to the method of JISK0070.
The amine value of the block copolymer before salt formation was determined by a method according to the method described in JIS K 7237.
The weight average molecular weight (Mw) of the block copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method of the present invention described above.
The glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation is measured by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII Nanotechnology) according to the method described in JIS K7121. It measured using.

(Synthesis Example 1: Preparation of Dispersant a)
Add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine and 1.0 part by mass of methyl isobutyrate were injected using a syringe. B block monomer 1-ethoxyethyl methacrylate (EEMA) 3.3 parts by mass, 2-hydroxyethyl methacrylate (HEMA) 18.2 parts by mass, 2-ethylhexyl methacrylate (EHMA) 4.2 parts by mass, methacryl 7.0 parts by mass of n-butyl acid (BMA), 24.7 parts by mass of benzyl methacrylate (BzMA), and 13.3 parts by mass of methyl methacrylate (MMA) were added dropwise using an addition funnel over 60 minutes. . After 30 minutes, 30.8 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, diluted with PGMEA to obtain a solid content solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the reaction was carried out for 7 hours. The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from a block containing a structural unit represented by the general formula (I) and a carboxy group-containing monomer The block copolymer A-1 (acid value 12 mgKOH / g, Tg44 degreeC) containing B block which has solvophilic property including was obtained. The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 8,100. The amine value was 110 mgKOH / g.
In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A-1 was dissolved in 29.35 parts by mass of PGMEA, and 1.59 parts by mass of phenylphosphonic acid (manufactured by Tokyo Chemical Industry) 0.1 mol) was added to 1 mol of the DMMA unit of the combined A-1, and the mixture was stirred at a reaction temperature of 30 ° C. for 20 hours to obtain a salt type block copolymer A-1 (dispersant a) solution. Specifically, the amine value after salt formation was calculated as follows.
Into an NMR sample tube, 1 g of a solution in which 9 parts by mass of salt-type block copolymer A-1 (solid after reprecipitation) and 91 parts by mass of chloroform-D1 NMR were mixed was put, and the ¹³ C-NMR spectrum was measured by nuclear magnetics. Using a resonance apparatus (manufactured by JEOL Ltd., FT NMR, JNM-AL400), measurement was performed under conditions of room temperature and 10,000 times of integration. Of the obtained spectral data, the integrated value of the carbon atom peak adjacent to the non-salt-formed nitrogen atom and the carbon atom peak adjacent to the salt-formed nitrogen atom at the terminal nitrogen site (amino group) From the ratio, the ratio of the number of amino groups that are salt-formed to the total number of amino groups is calculated, and is not different from the theoretical salt-forming ratio (the two acidic groups of all phenylphosphonic acids are in DMMA of the block copolymer A-1). It was confirmed that a salt was formed with the terminal nitrogen site).
The amine value after salt formation was calculated as 88 mgKOH / g by subtracting the amine value (22 mgKOH / g) of 0.20 mol of DMMA unit from the amine value 110 mgKOH / g before salt formation. The acid value of the block copolymer A-1 after salt formation is the same as that of the block copolymer A-1 before salt formation. Table 1 shows the acid value, amine value, and Tg of the block copolymer A-1 before salt formation and after salt formation.

(Synthesis Examples 2 to 4: Production of dispersants b to d)
In Synthesis Example 1, except that the content is changed to the contents shown in Table 1, the same as in Synthesis Example 1, the salt copolymers before salt formation A-2 to A-4 and the salt type block copolymer A-2 (Dispersant b) to A-4 (dispersant d) solutions were synthesized. In addition, 2.8 parts by mass of 1-ethoxyethyl methacrylate (EEMA) was used in Synthesis Example 2, 2.2 parts by mass in Synthesis Example 3, and 1.1 parts by mass in Synthesis Example 4. Table 1 shows the acid value, amine value, and Tg of the obtained block copolymer before and after salt formation.

(Synthesis Example 5: Preparation of dispersant e)
A 500 ml 4-neck separable flask was decompressed and dried, and then replaced with Ar (argon).
While flowing Ar, 100 g of dehydrated THF, 2.0 g of methyltrimethylsilyldimethylketene acetal, 0.15 ml of 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), and 0.2 g of mesitylene were added. Using a dropping funnel, 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-butyl methacrylate (BMA), 9.9 parts by mass of benzyl methacrylate (BzMA), methacrylic acid Methyl (MMA) 35.7 parts by mass was added dropwise over 45 minutes. As the reaction progressed, heat was generated, so the temperature was kept below 40 ° C by cooling with ice. After 1 hour, 26.7 g of dimethylaminoethyl methacrylate (DMMA) was added dropwise 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 A-5. The weight average molecular weight determined by GPC measurement (NMP LiBr 10 mM) was 8,350, and the amine value was 95 mgKOH / g.
In a 100 mL round bottom flask, 29.35 parts by mass of block copolymer A-5 was dissolved in 29.35 parts by mass of PGMEA, and 3.17 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.20 mol) with respect to 1 mol of DMMA unit of copolymer A-5, and stirred at a reaction temperature of 30 ° C. for 20 hours to obtain a salt type block copolymer A-5 (dispersant e) solution. It was. The amine value after salt formation was calculated in the same manner as in Synthesis Example 1. Table 1 shows the acid value, amine value, and Tg of the obtained block copolymer before and after salt formation.

(Synthesis Example 6: Preparation of dispersant f)
In Synthesis Example 5, instead of phenylphosphonic acid, 3.80 parts by mass of benzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) (benzyl chloride is 0.3 mol with respect to 1 mol of DMMA unit of block copolymer A-5) is used. A salt type block copolymer A-6 (dispersant f) solution was synthesized in the same manner as in Synthesis Example 5 except that. Table 1 shows the acid value, amine value, and Tg of the obtained block copolymer before and after salt formation.

(Synthesis Example 7: Preparation of Dispersant g)
In Synthesis Example 5, 13.4 parts by mass of 2-ethylhexyl methacrylate (EHMA), 14.3 parts by mass of n-butyl methacrylate (BMA), 9.9 parts by mass of benzyl methacrylate (BzMA), and methyl methacrylate ( MMA) 35.7 parts by mass n-butyl methacrylate (BMA) 7.6 parts by mass, methyl methacrylate (MMA) 32.9 parts by mass, and PME-1000 (methoxy polyethylene glycol monomethacrylate (polyethylene glycol) The number of chain repetitions n≈23), trade name Blemmer PME-1000, manufactured by NOF Co., Ltd. 39.9 parts by mass, dimethylaminoethyl methacrylate (DMMA) was replaced with 26.7 parts by mass, 19.6 parts by mass Except that it was used, the same procedure as in Synthesis Example 5 was followed, except that salt copolymer A-7 before salt formation and salt block were used. Copolymer A-7 was obtained (dispersing agent g) solution. The amine value after salt formation was calculated in the same manner as in Synthesis Example 1. Table 1 shows the acid value, amine value, and Tg of the obtained block copolymer before and after salt formation.

(Synthesis Example 8: Preparation of alkali-soluble resin A solution)
A mixed solution 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 into a polymerization tank containing 150 parts by mass of PGMEA at 100 ° C. for 3 hours in a nitrogen stream. did. After completion of dropping, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol are added to the obtained polymer solution and heated at 110 ° C. for 10 hours to react. Air was bubbled through the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into the main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has a solid content of 42.6 mass. %, Acid value 74 mgKOH / g, and weight average molecular weight 12000. The weight average molecular weight was measured with Shodex GPC System-21H (Polystyrene) using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070.

(Synthesis Example 9: Preparation of alkali-soluble resin B solution)
In Synthesis Example 8, instead of using 40 parts by mass of BzMA as a comonomer species at the time of polymerization, Synthesis Example 8 was used except that 20 parts by mass of styrene and 20 parts by mass of N-phenylmaleimide (Tokyo Chemical Industry Co., Ltd.) were used. Similarly, an alkali-soluble resin B solution was obtained. The solid content was 42.6% by mass, the acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

(Synthesis Example 10: Synthesis of blue color material 1)
(1) Synthesis of Intermediate 1 Referring to the method for producing Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, 15.9 g (inclusive) of Intermediate 1 represented by the following chemical formula (A) Rate 70%).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent and elemental analysis values: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(2) Synthesis of Blue Color Material 1 Intermediate 5.00 g (4.58 mmol) was added to 300 ml of water and dissolved at 90 ° C. to obtain Intermediate 2 solution. Next, 10.44 g (3.05 mmol) of phosphotungstic acid · n hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O (n = 30) manufactured by Nippon Inorganic Chemical Industry Co., Ltd. was added to 100 mL of water and stirred at 90 ° C. An aqueous phosphotungstic acid solution was prepared. The intermediate 2 solution was mixed with an aqueous phosphotungstic acid solution at 90 ° C., and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of blue color material 1 represented by the following chemical formula (B).
The obtained compound was confirmed to be the target compound from the following analysis results. (Molar ratio W / Mo = 100/0)
MS (ESI) (m / z): 510 (+), divalent, elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%); theoretical value (41.66%) (5.17%, 4.11%)
Further, it was confirmed by ³¹ P-NMR that the polyacid structure of phosphotungstic acid was maintained after the blue colorant 1 was obtained.

(Synthesis Example 11: Synthesis of Purple Color Material 2)
Acid Red 289 represented by the following formula (AR289; purple color material 1, manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 g was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. 3.85 g of polyaluminum chloride (“trade name: Takibaine # 1500” manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5 mass%, alumina content 23.5 mass%) in 200 ml of water The mixture was stirred at 80 ° C. to prepare a polyaluminum chloride aqueous solution. The prepared polyaluminum chloride aqueous solution was added dropwise to the dye solution at 80 ° C. over 15 minutes, and further stirred at 80 ° C. for 1 hour. The formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 6.30 g (yield 96.2%) of a rhodamine acid dye metal lake color material (purple color material 2).

(Synthesis Example 12: Synthesis of Latent Antioxidant (Compound a))
A phenol compound represented by the following chemical formula (4) 0.01 mol, di-tert-butyl dicarbonate 0.05 mol and pyridine 30 g were mixed, and 0.025 mol of 4-dimethylaminopyridine was added at room temperature under a nitrogen atmosphere. Stir for 3 hours at ° C. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added to perform oil / water separation. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powder crystals were dried under reduced pressure at 60 ° C. for 3 hours to obtain a latent antioxidant (compound a) represented by the chemical formula (a). The structure of the obtained latent antioxidant was confirmed by IR and NMR.

Example 1
(1) Production of Colorant Dispersion B1 6.23 parts by mass of Dispersant a Solution of Synthesis Example 1 as a dispersant and C.I. I. CI Pigment Blue 15: 6 (trade name FASTOGEN BLUE A510 manufactured by DIC Corporation) is 6.42 parts by mass, and C.I. I. Pigment Violet 23 (trade name: Hostaperm Violet RL-NF manufactured by Clariant) 1.61 parts by mass, C.I. I. CI Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 manufactured by DIC Corporation) 4.97 parts by mass, 14.59 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8, 66.12 parts by mass of PGMEA, Put 100 parts by mass of 2.0 mm zirconia beads into a mayonnaise bin, shake as a preliminary crushing with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour, then take out the 2.0 mm zirconia beads and remove the particles. 200 parts by mass of zirconia beads having a diameter of 0.1 mm was added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a colorant dispersion liquid B1.

(2) Production of Colored Resin Composition B1 for Color Filter 8.18 parts by mass of colorant dispersion B1 obtained in (1) above and 1.08 mass of alkali-soluble resin A solution obtained in Synthesis Example 8 Parts, polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) 0.71 parts by mass, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF Corporation) 0.07 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Hikari Initiator: 0.04 parts by mass of trade name Irgacure 369 (IRG369), manufactured by BASF), 0.02 parts by mass of diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., “DETX-S” (DETX)), oxy 0.02 parts by mass of a muester initiator (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., “TR-PBG-3057” (PBG3057)), a fluorosurfactant (trade name: MegaFuck F559, manufactured by DIC Corporation) 0.07 part by mass, silane coupling agent (trade name KBM-503, manufactured by Shin-Etsu Silicone) 0.07 part by mass, mercapto compound (pentaerythritol tetrakis (3-mercaptobutyrate)) 0.05 part by mass, PGMEA 58 .85 parts by mass and 3.92 parts by mass of 3-methoxy-3-methyl-1-butyl acetate were added to obtain a colored resin composition B1 for color filters.
(3) Formation of colored layer The colored resin composition B1 obtained in (2) above is formed on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm. After applying using a spin coater, it is dried at 80 ° C. for 3 minutes using a hot plate, irradiated with 60 mJ / cm ² of ultraviolet light using an ultrahigh pressure mercury lamp, and further post-baked for 30 minutes in a 230 ° C. clean oven. Thus, the colored layer B1 was formed by adjusting the film thickness so that the film thickness after curing was 2.50 μm.

(Examples 2 to 12, Comparative Examples 1 to 4)
(1) Production of Color Material Dispersions B2 to B9 and CB1 to CB4 In Examples 2 to 6 and Comparative Example 1, in (1) of Example 1, as shown in Table 2, each of the dispersant a solution Instead, the same manner as in (1) of Example 1 except that the type and amount of dispersant were changed so that the solid content was the same part by mass, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. Thus, color material dispersions B2 to B6 and color material dispersion CB1 were obtained.
Moreover, in Examples 7-9, as shown in Table 2 in Example 3 (1), except that the type and amount of color material were changed, the same as (1) in Example 3 Color material dispersions B7 to B9 were obtained.
Moreover, in Comparative Examples 2-4, as shown in Table 2 in Example 1 (1), instead of the dispersant a solution, the type and amount of the dispersant used are the same mass parts with the same solid content. In the same manner as in (1) of Example 1 except that the amount of PGMEA was adjusted so that the total amount was 100 parts by mass, and the type and amount of color material were changed, the color material dispersion CB2 ~ CB4 was obtained.
(2) Production of Colored Resin Compositions B2 to B12 and CB1 to CB4 for Color Filter In Examples 2 to 9 and Comparative Examples 1 to 4, respectively, instead of the color material dispersion B1 in (2) of Example 1 As shown in Table 2, using the colorant dispersions B2 to B9 and CB1 to CB4, the P / V ratio is set to be 2.50 μm by the method (3) of Example 1. Except having adjusted the quantity of alkali-soluble resin so that it might become the value shown in Table 2, it carried out similarly to (2) of Example 1, and obtained colored resin composition B2-B9, CB1-CB4 for color filters. .
Further, in Example 10, in the same manner as in Example 3 (2) except that 0.03 part by mass of the antioxidant IRGANOX 1010 (manufactured by BASF) was added in Example 3, for color filters. A colored resin composition B10 was obtained.
In Example 11, instead of using the alkali-soluble resin A solution in Example 3, the alkali-soluble resin B solution obtained in Synthesis Example 9 was used, and the antioxidant IRGANOX 1010 (manufactured by BASF) 0 A colored resin composition B11 for color filters was obtained in the same manner as (2) of Example 3 except that 0.03 parts by mass were added.
Moreover, in Example 12, as shown in Table 2 for the photoinitiator in Example 11, instead of 0.04 parts by mass of IRG369, an oxime ester photoinitiator (manufactured by Changzhou Strong Electronic New Materials, A colored resin composition B12 for color filters was obtained in the same manner as (2) of Example 11 except that 0.04 parts by mass of “TR-PBG-365” (PBG365) was used.
In the combination of the color materials of Comparative Examples 3 to 4, the chromaticity of x = 0.130 and y = 0.119 can be realized with the film thickness of 2.5 μm by the method (3) of Example 1. A colored resin composition could not be prepared.
(3) Formation of colored layer In (1) of Example 1, (3) in Example 1 except that the colored resin compositions B2 to B12 and CB1 to CB2 were used instead of the colored resin composition B1, respectively. ), Colored layers B2 to B12 and CB1 to CB2 were obtained.

Here, each abbreviation in the table is as follows.
PB15: 3: C.I. I. Pigment Blue 15: 3 (trade name: Chromo Fine Blue A-220JC, manufactured by Dainichi Seika Kogyo Co., Ltd.)
Blue color material 1: Blue color material 1 of Synthesis Example 10
Purple color material 1: Acid Red 289 (AR289, manufactured by Tokyo Chemical Industry Co., Ltd.)
Purple color material 2: Purple color material 2 of Synthesis Example 11
PG58: C.I. I. Pigment Green 58 (trade name: FASTOGEN GREEN A110, manufactured by DIC Corporation)
Byk161: trade name Disperbyk-161 (by Big Chemie, urethane dispersant, solid content 30% by mass)
Byk2001: trade name Disperbyk-2001 (by Big Chemie, polymer having a structural unit represented by general formula (I), solid content: 46% by mass)
Solvent A: Propylene glycol monomethyl ether acetate (PGMEA)
Solvent B: 3-methoxy-3-methyl-1-butyl acetate

(Examples 13 to 15)
(1) Production of Coloring Material Dispersions B13 to B15 In Examples 13 to 15, in (1) of Example 3, as shown in Table 3, the type and blending amount of the coloring material were changed, and the total Color material dispersions B13 to B15 were obtained in the same manner as (1) of Example 3 except that the amount of PGMEA was adjusted to 100 parts by mass.
(2) Production of Colored Resin Compositions for Color Filters B13 to B15 The above color material dispersions B13 to B15 are used in place of the color material dispersion B3 in (2) of Example 12, respectively (3) of Example 1. In the same manner as (2) of Example 12 except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio would be the value shown in Table 3 in order to obtain a film thickness of 2.50 μm by the above method. Thus, colored resin compositions B13 to B15 for color filters were obtained.
(3) Formation of colored layer In the same manner as (3) of Example 12, except that the colored resin composition B13 to B15 were used in place of the colored resin composition B12 in (3) of Example 12. Thus, colored layers B13 to B15 were obtained.

(Comparative Examples 5-7)
(1) Production of Color Material Dispersions CB5 to CB7 In Comparative Examples 5 to 7, in (1) of Example 1, as shown in Table 3, instead of the dispersant a solution, the type and use of the dispersant The amount was changed so that the solid content was the same part by mass, and as shown in Table 3, the color material type and blending amount were changed, and the amount of PGMEA was adjusted so that the total amount was 100 parts by mass. In the same manner as in Example 1 (1), colorant dispersions CB5 to CB7 were obtained.
(2) Production of Colored Resin Compositions for Color Filters CB5 to CB7 The above color material dispersions CB5 to CB7 were used in place of the color material dispersion B3 in (2) of Example 12, respectively (3) of Example 1. In the same manner as (2) of Example 12 except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio would be the value shown in Table 3 in order to obtain a film thickness of 2.50 μm by the above method. Thus, colored resin compositions for color filters CB5 to CB7 were obtained.
(3) Formation of colored layer In the same manner as (3) of Example 12, except that the colored resin compositions CB5 to CB7 were used instead of the colored resin composition B12 in Example 12 (3). Thus, colored layers CB5 to CB7 were obtained.

Here, each abbreviation in the table is as follows.
PG36: C.I. I. Pigment Green 36 (trade name: FASTOGEN GREEN 2YK-50, manufactured by DIC Corporation)
PG7: C.I. I. Pigment Green 7 (trade name: Chromo Fine Green 6428EC, manufactured by Dainichi Seika Kogyo)

(Examples 16 to 33)
(1) Production of Coloring Material Dispersions B16 to B33 In Examples 16 to 33, the types and blending amounts of the coloring materials were changed as shown in Table 4 in Example 3 (1). Color material dispersions B16 to B33 were obtained in the same manner as in Example 3 (1) except that the amount of PGMEA was adjusted to 100 parts by mass.
(2) Production of Colored Resin Compositions B16 to B33 for Color Filter The above color material dispersions B16 to B33 are used in place of the color material dispersion B3 in (2) of Example 12, respectively (3) of Example 1. Except that the amount of the alkali-soluble resin was adjusted so that the P / V ratio would be the value shown in Table 4 in order to obtain a film thickness of 2.80 μm by the above method, the same as (2) of Example 12 Thus, colored resin compositions B16 to B33 for color filters were obtained.
(3) Formation of colored layer In (3) of Example 12, in the same manner as (3) of Example 12 except that the colored resin compositions B16 to B33 were used instead of the colored resin composition B12, respectively. Thus, colored layers B16 to B33 were obtained.

ここで、表中各略号は、以下の通りである。
ＰＢ１６ ：Ｃ．Ｉ．ピグメントブルー１６（商品名：ヘリオゲンブルー Ｄ７４９０ ＢＡＳＦ製)

Here, each abbreviation in the table is as follows.
PB16: C.I. I. Pigment Blue 16 (Product name: Heliogen Blue D7490 manufactured by BASF)

(Example 34)
(1) Production of colorant dispersion
6.23 parts by mass of the dispersant c solution of Synthesis Example 3 as a dispersant and C.I. I. Pigment Blue 15: 6 (trade name FASTOGEN BLUE A510 manufactured by DIC Corporation) is 13.0 parts by mass, the alkali-soluble resin A solution obtained in Synthesis Example 8 is 14.59 parts by mass, and PGMEA is 66.20 parts by mass. Part, 100 parts by weight of zirconia beads having a particle size of 2.0 mm are put into a mayonnaise bin, shaken with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour as a preliminary crushing, and then taken out of zirconia beads having a particle size of 2.0 mm In addition, 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm were added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a blue color material dispersion b1.
In the blue color material dispersion b1, C.I. I. Instead of using 13.0 parts by mass of Pigment Blue 15: 6, C.I. I. A purple color material dispersion v1 was obtained in the same manner as in the blue color material dispersion b1 except that 13.0 parts by mass of Pigment Violet 23 (trade name: Hostaperm Violet RL-NF manufactured by Clariant) was used.
In the blue color material dispersion b1, C.I. I. Instead of using 13.0 parts by mass of Pigment Blue 15: 6, C.I. I. A green color material dispersion g1 was obtained in the same manner as the blue color material dispersion b1 except that 13.0 parts by mass of Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100 DIC Corporation) was used.

(2) Production of colored resin composition B34 for color filter 4.00 parts by mass of blue color material dispersion b1 obtained in (1) above, 1.01 parts by mass of purple color material dispersion v1, and green color material 3.12 parts by mass of dispersion g1, 1.08 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8, and 0 polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) .71 parts by mass, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (photoinitiator: trade name Irgacure 907 (IRG907), manufactured by BASF Corp.) 0.07 Parts by mass, 0.04 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator: trade name Irgacure 369 (IRG369), manufactured by BASF) Sandton (Nippon Kayaku Co., Ltd., "DETX-S" (DETX)) 0.02 parts by mass, oxime ester-based initiator (Changzhou Power Electronics New Materials Co., Ltd., "TR-PBG-3057" (PBG3057)) 0.02 part by mass, 0.07 part by mass of a fluorosurfactant (trade name MegaFuck F559, manufactured by DIC Corporation), 0.07 part by mass of a silane coupling agent (trade name KBM-503, manufactured by Shin-Etsu Silicone) Parts, mercapto compound (pentaerythritol tetrakis (3-mercaptobutyrate)) 0.05 parts by mass, PGMEA 58.85 parts by mass, 3-methoxy-3-methyl-1-butylacetate 3.92 parts by mass, A colored resin composition B34 for color filters was obtained.
(3) Formation of colored layer In (3) of Example 1, coloring was performed in the same manner as (3) of Example 1 except that the colored resin composition B34 was used instead of the colored resin composition B1. Layer B34 was obtained.
The obtained colored resin composition B34 for color filters has the same composition as the colored resin composition B3 for color filters of Example 3, and the evaluation results of the colored resin composition B34 for color filters and the colored layer B34 are as follows: It became the same as the evaluation result of colored resin composition B3 for color filters, and colored layer B3.

(Examples 35-40)
(1) Production of Colorant Dispersion B39 In Example 39, as shown in Table 5 in Example 1 (1), solid content was obtained by using Dispersant g solution instead of Dispersant a solution. Were changed to have the same mass part, and a colorant dispersion B39 was obtained in the same manner as (1) of Example 1 except that the amount of PGMEA was adjusted so that the total would be 100 parts by mass.
(2) Production of colored resin composition B35 to B40 for color filter In Example 35, as shown in Table 5 for the photoinitiator in Example 3, IRG369 was replaced with 0.04 parts by mass of oxime ester. 0.02 parts by mass of a photoinitiator (trade name: Irgacure OXE 01 (OXE01), manufactured by BASF) and PGB3057 instead of 0.02 parts by mass, an oxime ester-based initiator (trade name: Irgacure OXE 02 (OXE02) A colored resin composition B35 for color filter was obtained in the same manner as (2) of Example 3 except that 0.04 parts by mass of BASF) was used.
Moreover, in Example 36, instead of 0.03 part by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF) in Example 10, the antioxidant (trade name ADK STAB AO-40 (AO- 40), manufactured by ADEKA) Except for using 0.03 parts by mass, a colored resin composition B36 for color filters was obtained in the same manner as (2) of Example 10.
Moreover, in Example 37, instead of 0.03 part by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF) in Example 10, the latent antioxidant (Compound a) of Synthesis Example 12 was used. A colored resin composition B37 for color filters was obtained in the same manner as (2) of Example 10 except that 0.03 parts by mass were used.
In Example 38, instead of adding 0.03 part by mass of the antioxidant (trade name IRGANOX 1010 (1010), manufactured by BASF) in Example 10, an ultraviolet absorber (benzotriazole compound, trade name) A colored resin composition for color filter B38 was obtained in the same manner as (2) of Example 10 except that 0.03 part by mass of TINUVIN 329 BASF was added.
In Example 39, a colored resin composition for a color filter was obtained in the same manner as in (2) of Example 3 except that the color material dispersion B39 was used instead of the color material dispersion B3 in Example 3. B39 was obtained.
In Example 40, the alkali-soluble resin obtained in Synthesis Example 9 was used in Example 35, except that the color material dispersion B39 was used instead of the color material dispersion B3 and the alkali-soluble resin A solution was used. Using solution B, 0.03 parts by mass of antioxidant (trade name ADK STAB AO-40 (AO-40), manufactured by ADEKA) and UV absorber (benzotriazole compound, product name TINUVIN 329 manufactured by BASF) 0.03 A colored resin composition B40 for a color filter was obtained in the same manner as (2) of Example 35 except for adding part by mass.
(3) Formation of colored layer In (3) of Example 1, in the same manner as (3) of Example 1 except that the colored resin compositions B35 to B40 were used instead of the colored resin composition B1, respectively. As a result, colored layers B35 to B40 were obtained.

[Evaluation method]
<Evaluation of dispersibility of colorant dispersion>
For the colorant dispersions obtained in Examples and Comparative Examples, the viscosity immediately after preparation and after storage for 30 days at 25 ° C. are measured, the rate of change in viscosity is calculated from the viscosity before and after storage, and the viscosity stability is evaluated. did. The viscosity was measured at 25.0 ± 0.5 ° C. using a vibration viscometer.
(Viscosity stability evaluation criteria)
A: Change rate of viscosity before and after storage is less than 10% B: Change rate of viscosity before and after storage is 10% or more and less than 20% C: Change rate of viscosity before and after storage is 20% or more and less than 30% D: Before and after storage Viscosity change rate is 30% or more However, this is a value when the color material is 13% by mass with respect to the total mass including the solvent of the color material dispersion.
Even if the evaluation result is C, the color material dispersion can be used practically. However, if the evaluation result is B, the color material dispersion is better. If the evaluation result is A, the color material dispersion is excellent in dispersion stability. Are better.

<Optical performance evaluation, contrast evaluation>
The contrast, chromaticity (x, y), and luminance (Y) of the colored layers obtained in Examples and Comparative Examples were measured using Otsuka Electronics' spectroscopic characteristic measurement device LCF-1500M and Aisaka Electric's contrast measurement device CT-1B. Measured.
(Contrast evaluation criteria)
-Value when C is light source and y is 0.038 to 0.070 AA: over 5000 A: 3500-4999
B: 1500-3499
C: less than 1500. Value when y is 0.071 to 0.110 with C light source AA: over 6000 A: 4000 to 5999
B: 2000-3999
C: less than 2000. Value when y is 0.111 to 0.140 with C light source AA: over 7000 A: 4500-6999
B: 2500-4499
C: less than 2500 · Value when y is 0.141 to 0.180 with C light source AA: Exceeding 7500 A: 5000 to 7499
B: 3000-4999
C: less than 3000 If the above evaluation criteria are AA, A or B, it is evaluated as good contrast and can be used practically without problems, but if the evaluation result is A and further AA, the effect is more excellent.

<Solvent resolubility evaluation>
The tip of a glass substrate having a width of 0.5 cm and a length of 10 cm was immersed in the colored resin composition for a color filter obtained in Examples and Comparative Examples, and applied to a 1 cm portion of the glass substrate. The pulled glass substrate was placed in a thermo-hygrostat so that the glass surface was horizontal, and dried at a temperature of 23 ° C. and a humidity of 80% RH for 10 minutes. Next, the glass substrate to which the dried coating film was adhered was immersed in PGMEA for 15 seconds. At this time, the redissolved state of the dried coating film was visually discriminated and evaluated.
(Solvent re-solubility evaluation criteria)
AA: The dried coating film was completely dissolved in 8 seconds or less. A: The dried coating film was completely dissolved. B: A flake of the dried coating film was formed in the solvent, and the solution was colored. C: The dried coating film was dissolved in the solvent. The flakes did not occur and the solution did not color. If the above evaluation criteria were AA, A or B, it was evaluated that the solvent resolubility was good and could be used practically without any problem, but the evaluation result was A and further AA. Is more effective.

<Development residue evaluation>
The colored resin compositions for color filters obtained in the examples and comparative examples were respectively applied to a spin coater on a 100 mm × 100 mm glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) with a thickness of 0.7 mm. After being applied, it was dried at 60 ° C. for 3 minutes using a hot plate to form a colored layer having a thickness of 2.5 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. After observing the unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer by visual observation, the glass substrate is thoroughly wiped with a lens cleaner (trade name Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.), The coloring degree of the lens cleaner was visually observed.
(Development residue evaluation criteria)
AA: Even in the same evaluation with a colored layer having a thickness of 3.5 μm, no development residue was visually confirmed and the lens cleaner was not colored at all. A: No development residue was visually confirmed, and the lens cleaner was completely colored. B: Development residue was not visually confirmed, and the color of the lens cleaner was slightly confirmed. C: Development residue was visually confirmed, and the color of the lens cleaner was confirmed. D: Development residue was visually confirmed. When the above evaluation criteria are AA, A, B, or C, it can be used practically, but if the evaluation result is B, further A, and further AA, the effect is more excellent. ing.

<Development resistance evaluation>
The colored resin compositions for color filters obtained in Examples and Comparative Examples were each applied on a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. After heating and drying on an 80 ° C. hot plate for 3 minutes, ultraviolet rays of 40 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp. The film thickness at this point is measured and set to T1 (μm). Thereafter, shower development was performed using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The film thickness after development is measured and set to T2 (μm). T2 / T1 × 100 (%) was calculated.
(Development resistance evaluation criteria)
AA: 98% or more A: 95% or more and less than 98% B: 90% or more and less than 95% C: less than 90% Although the evaluation results are AA, A, and B, they can be used practically. AA is more effective.

<Development chip>
Spin the colored resin composition for color filter obtained in each example and each comparative example on a 100 mm × 100 mm glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) with a thickness of 0.7 mm. After coating using a coater, the number of rotations is adjusted to the film thickness shown in the table after post baking (30 minutes in a 230 ° C clean oven) by drying at 60 ° C for 3 minutes using a hot plate. Then, a colored layer was formed. This colored layer was irradiated with 30 mJ / cm ² of ultraviolet rays using a super high pressure mercury lamp through a photomask having a mask opening width of 80 μm and a mask light shielding width of 160 μm. The glass plate on which the colored layer was formed was shower-developed for 100 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The developed substrate was observed with an optical microscope, and the number of chips on the edge portion of the colored layer in the range of 50 mm × 50 mm was measured.
(Development chip evaluation criteria)
AA: No chipping A: Less than 20 B: 20 or more and less than 50 C: 50 or more If the development chip evaluation standard is AA, A or B, it can be used practically, but the evaluation result is A, and further AA If there is, it is more effective.

<Mura>
Spin the colored resin composition for color filter obtained in each example and each comparative example on a 100 mm × 100 mm glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) with a thickness of 0.7 mm. After coating using a coater, drying was performed at 60 ° C. for 3 minutes using a hot plate, thereby adjusting the number of revolutions so that the film thickness described in the table was obtained after post-baking to form a colored layer. The colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using a super high pressure mercury lamp through a photomask having a mask opening width of 80 μm and a mask light shielding width of 160 μm. The glass plate on which the colored layer was formed was shower-developed for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. Next, the unevenness of the colored layer is visually observed under a projector on the substrate obtained by post-baking the colored substrate in a clean oven at 230 ° C. for 30 minutes, and the edge portion of the colored layer in the range of 50 mm × 50 mm is further observed with an optical microscope. The number of voids was measured.
(Evaluation criteria for unevenness)
AA: No unevenness, no gap at the edge portion A: No unevenness, less than 20 gaps at the edge portion B: Some unevenness was observed C: Unevenness was observed as a whole The unevenness evaluation standard was AA or A If there is, it can be used practically, but if the evaluation result is A and further AA, the effect is more excellent.

[Summary of results]
From the result of a table, Examples 1-33 which combined the purple color material and PG59 with the blue color material, and also the dispersing agent which is a polymer which has a structural unit represented by general formula (I). The colorant dispersions No. 39 and No. 39 were found to have good viscosity stability. On the other hand, it was revealed that the color material dispersion of Comparative Example 1 in which a blue color material, a purple color material, and PG59 were combined with a urethane dispersant has poor viscosity stability.
Moreover, the dispersion material which is a polymer which has a structural unit represented by general formula (I) is used for the color material dispersion liquid of the comparative examples 2 and 5-7 which combined the conventional green color material with the blue color material. However, it was shown that the viscosity stability is poor.

Further, for the color filter of Examples 1 to 40, in which a purple color material and PG59 are combined with a blue color material, and further, a dispersant that is a polymer having a structural unit represented by the general formula (I) is combined. It was revealed that the colored resin composition is a colored resin composition for a color filter that can form a colored layer with improved solvent resolubility and an expanded blue reproduction range. Moreover, it was also clarified that the colored layers using the photosensitive colored resin compositions of Examples 1 to 40 each suppress the occurrence of development chipping and unevenness.
On the other hand, Comparative Example 1 in which a blue color material, a purple color material, PG59, and a urethane-based dispersant are combined has a solvent re-solubility as compared with an example having the same chromaticity coordinates (x, y). Inferior, contrast, further development residue, development resistance, development chipping and unevenness were inferior. When a urethane-based dispersant is combined with the color material combination, the dispersibility and dispersion stability are poor, so the color material is not well surrounded by the dispersant and is adsorbed by the re-dissolvable solvent. It is presumed that the coloring material is hardly washed away.
Moreover, in the color materials of Comparative Examples 3 to 4, it was impossible to prepare a colored resin composition that could realize chromaticity of x = 0.130 and y = 0.119.
Further, in Comparative Examples 2 and 5 to 7, compared with Examples having the same chromaticity coordinates (x, y), the P / V ratio in the colored resin composition tends to increase and the solvent resolubility is inferior. It was. Further, in Comparative Examples 2 and 5-7, development chipping and unevenness were likely to occur as compared with Examples having the same chromaticity coordinates (x, y).
The coloring materials of the colored resin compositions of Examples 1 to 40 and the ratio thereof are as follows (the XYZ color system of JIS Z8701 in which the film thickness is 2.8 μm or less and the color is measured with a C light source with a single pixel) In the chromaticity coordinates, x = 0.120 or more and 0.147 or less, y = 0.038 or more and 0.180 or less in the color material of the cured film capable of displaying a color space, blue color material, purple color material, And the ratio of PG59 is maintained, and the colorant concentration (total colorant mass / solvent-containing colorant dispersion) is 1 / 60,000 of the colorant concentration of the cured film (total mass of the colorant / total mass of the solid content of the cured film). When the diluted test color material dispersion having a total liquid mass) is prepared, and the diluted test color material dispersion is put into a cell having a thickness of 1 cm and the spectral transmittance is measured, the average in the range of 280 nm to 360 nm The transmittance is 42% or more). On the other hand, in the colored resin compositions of Comparative Examples 2 and 5 to 7, the average transmittance in the range of 280 nm to 360 nm was less than 41%.

Among the examples, it was clarified that, in the examples including both the maleimide structure having a hydrocarbon ring and the styrene structure as the alkali-soluble resin, a colored resin composition with improved suppression of development residue can be obtained.
Further, it was clarified that when two oxime ester photoinitiators were used in combination, a colored resin composition having improved development resistance was obtained.

Among the examples, in the examples in which the oxime ester photoinitiator and the antioxidant were combined, a colored resin composition with improved development chipping and unevenness suppression effect was obtained. In the example in which the antioxidant was added, it was revealed that a colored layer with improved contrast was obtained. The contrast of Examples 10 to 12 was A close to AA. Among them, in Example 36 using a hindered phenol antioxidant having a molecular weight of 500 or less and a molecular weight per phenolic hydroxyl group of 200 equivalents or less, a colored layer having high contrast was obtained.
Further, in Example 37 using the latent antioxidant, a colored resin composition with improved unevenness suppression effect was obtained, and a colored layer with good development adhesion and improved contrast was obtained.
Further, in Example 38 in which the oxime ester photoinitiator and the ultraviolet absorber were combined, a colored resin composition with improved development chipping and unevenness suppression effect was obtained. In the example in which the ultraviolet absorber was added, a colored layer with improved contrast was obtained.
In addition, an alkali-soluble resin containing both a maleimide structure having a hydrocarbon ring and a styrene structure is used, and an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having diphenyl sulfide are used in combination. Example 40 using a combination of a hindered phenolic antioxidant having a molecular weight of 500 or less and a molecular weight per phenolic hydroxyl group of 200 equivalents or less and an ultraviolet absorber, A colored resin composition with improved unevenness suppression and development resistance was obtained, and a colored layer with improved contrast was obtained.

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

Claims (14)

A color material dispersion containing a color material, a dispersant, and a solvent,
The color material is a blue color material, a purple color material, and C.I. I. Including Pigment Green 59,
The dispersant is a polymer having a structural unit represented by the following general formula (I):
Color material dispersion for blue colored layer of color filter.

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R ² and R ³ may combine with each other to form a ring structure.) The color material dispersion for a blue colored layer of a color filter according to claim 1, wherein the purple color material is contained in the color material in an amount of 1% by mass to 45% by mass. The blue color material is C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 15: 3, C.I. I. The color material dispersion for a blue colored layer of a color filter according to claim 1 or 2, which is at least one selected from the group consisting of CI Pigment Blue 15: 4 and a triarylmethane-based lake color material. The purple color material is C.I. I. The blue coloration of the color filter according to any one of claims 1 to 3, which is at least one selected from the group consisting of CI Pigment Violet 23, an anthraquinone color material, a cyanine color material, and a xanthene color material. Color material dispersion for layer . A colored resin composition for a color filter containing a coloring material, a dispersant, a binder component, and a solvent,
The color material is a blue color material, a purple color material, and C.I. I. Including Pigment Green 59,
The dispersant is a polymer having a structural unit represented by the following general formula (I):
A colored resin composition for a blue colored layer of a color filter.

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, A is a divalent linking group, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon that may contain a hetero atom. Represents a group, and R ² and R ³ may combine with each other to form a ring structure.) The colored resin composition for a blue colored layer of a color filter according to claim 5, wherein the purple color material is contained in the color material in an amount of 1% by mass to 45% by mass. The blue color material is C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 15: 3, C.I. I. The colored resin composition for a blue colored layer of a color filter according to claim 5 or 6, wherein the colored resin composition is one or more selected from the group consisting of CI Pigment Blue 15: 4 and a triarylmethane-based lake color material. The purple color material is C.I. I. The blue coloration of the color filter according to any one of claims 5 to 7, which is at least one selected from the group consisting of CI Pigment Violet 23, an anthraquinone color material, a cyanine color material, and a xanthene color material. Colored resin composition for layers . The said binder component contains alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and also contains a mercapto compound, For the blue colored layer of the color filter of any one of Claims 5-8. Colored resin composition. The colored resin composition for a blue colored layer of a color filter according to claim 9, wherein the photoinitiator contains an oxime ester and further contains an antioxidant. The colored resin composition for a blue colored layer of a color filter according to claim 9 or 10, wherein the photoinitiator contains at least two oxime esters. A cured film having chromaticity coordinates in the XYZ color system of JIS Z8701 measured using a C light source in the range of x = 0.120 to 0.147 and y = 0.038 to 0.180. The colored resin composition for a blue colored layer of a color filter according to any one of claims 5 to 11, which can be formed. It is a color filter provided with at least a transparent substrate and the colored layer provided on the said transparent substrate, Comprising: At least 1 of the said colored layer is a blue colored layer of the color filter of any one of Claims 5-12 A color filter having a blue colored layer that is a cured product of the colored resin composition.   A display device comprising the color filter according to claim 13.

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