JP6692184B2 - Photosensitive colored resin composition for color filter, color filter, display device - Google Patents

Description

  The present invention relates to a photosensitive colored resin composition for a color filter (hereinafter sometimes abbreviated as “photosensitive colored resin composition” or “colored resin composition”), a color filter, and a display device.

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

Here, the color filter is generally a transparent substrate, a colored layer formed on the transparent substrate, which is composed of colored patterns of three primary colors of red, green, and blue, and a transparent substrate on the transparent substrate so as to partition each colored pattern. And the formed light shielding part.
As a method of forming a colored layer in a color filter, a pigment dispersion method having excellent properties on average is most widely adopted among them from the viewpoints of spectral characteristics, durability, pattern shape, accuracy and the like. A color filter using the pigment dispersion method is usually a glass substrate on which a colored resin composition obtained by adding a binder resin, a photopolymerizable compound and a photoinitiator to a pigment dispersion liquid in which a pigment is dispersed with a dispersant or the like is added. After coating and drying, exposure is performed using a photomask and development is performed to form a colored pattern, and heating is performed to fix the pattern to form a colored layer. These steps are repeated for each color to form a color filter.

  With regard to color filters as well, the demand for higher brightness, higher contrast, and improved color reproducibility is increasing. Patterning becomes difficult because less components are required. Further, in order to improve the productivity of the color filter, the integrated exposure dose required for patterning is reduced, and how to secure the curability required for patterning is a major issue.

As a method for obtaining a colored resin composition capable of achieving high sensitivity, it has been proposed to use an oxime ester compound having one oxime ester group in the molecule as a photopolymerization initiator (for example, Patent Document 1).
Further, Patent Document 2 proposes, as a photosensitive resin composition capable of achieving high sensitivity, the use of an oxime ester compound having two oxime ester groups in the molecule as a photopolymerization initiator.

Japanese Patent No. 3992725 Chinese Patent Application Publication No. 104614940

  Conventionally, even if an oxime ester compound, which has been considered to be capable of achieving high sensitivity, is used, for example, when the colorant concentration is high or the integrated exposure amount is low, the curability becomes insufficient and the residual film rate becomes There was a problem that it tended to be insufficient.

The present invention has been made in view of the above circumstances, and has, for example, excellent curability even when the coloring material concentration is high or the integrated exposure amount is small, and the residual film rate is high. A colored resin composition, a color filter formed using the photosensitive colored resin composition for a color filter, and a display device having excellent display characteristics by using the color filter are provided.
Furthermore, the subject of this invention is providing the coloring composition for color filters with high sensitivity (so-called high residual film rate).
Here, "highly sensitive" means that the radical generation amount of the polymerization initiator contained in the coloring composition is large. In the case of a photopolymerization initiator, if the photoreceptivity is high, the amount of radicals generated is large and the sensitivity is high.
When the colored layer having a predetermined pattern is manufactured, the colored layer is formed by irradiating light and curing to leave only the irradiated portion after development. When the sensitivity of the coloring composition is high, since the curing is sufficiently advanced, the amount of decrease in the film thickness due to the development of the light-irradiated portion is small, and the film thickness hardly changes. On the other hand, when the sensitivity of the coloring composition is low, the curing is insufficient and the film thickness is reduced by being developed with a developing solution, so that the amount of the film thickness of the portion irradiated with light is greatly reduced by the development.
Therefore, the sensitivity of the coloring composition can be evaluated by measuring the residual film ratio (the ratio of the film thickness of the coating film after development to the film thickness of the coating film after exposure of the coloring composition).

  The present inventors have conducted intensive studies to achieve the above-mentioned object, and as a result of including a specific photoinitiator in the photosensitive colored resin composition, they found that the above-mentioned problems can be solved, and completed the present invention. Came to do.

That is, the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The photoinitiator contains a compound represented by the following general formula (A), which provides a photosensitive colored resin composition for a color filter.

［一般式（Ａ）中、Ｒ^１１は炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基である。Ｒ^１２は炭素数１〜１２の基である。Ｒ^１３は一般式（Ｂ）又は一般式（Ｃ）で表される基である。Ｙは硫黄原子又は酸素原子である。］

[In general formula (A), R < ¹¹ > is a C1-C5 alkyl group or a C1-C5 alkoxy group. R ¹² is a group having 1 to ¹² carbon atoms. R ¹³ is a group represented by the general formula (B) or the general formula (C). Y is a sulfur atom or an oxygen atom. ]

［一般式（Ｂ）及び一般式（Ｃ）において、Ｚは酸素原子、硫黄原子又は−Ｎ（Ｒ_ｚ）−（Ｒ_ｚは水素原子又は炭素数１〜５のアルキル基）であり、一般式（Ｂ）及び一般式（Ｃ）において各水素原子は置換されていてもよい。］

[In General Formula (B) and General Formula (C), Z is an oxygen atom, a sulfur atom, or -N (R _z )-(R _z is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); Each hydrogen atom in (B) and general formula (C) may be substituted. ]

Further, the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is a curable photosensitive color resin composition for a color filter as described above. The present invention provides a color filter having a colored layer made of a material.
The present invention also provides a display device including the above color filter.

  According to the present invention, a photosensitive colored resin composition having excellent curability and a high residual film ratio, a color filter formed using the photosensitive colored resin composition for the color filter, and the color filter By using, it is possible to provide a display device having excellent display characteristics.

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

  Hereinafter, the present invention will be described, but the present invention is not limited to the following specific forms and can be arbitrarily modified within the scope of the technical idea.

Hereinafter, the photosensitive colored resin composition for a color filter, 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 non-visible regions and further 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) acrylic” means each of acrylic and methacrylic, and “(meth) acrylate” means each of acrylate and methacrylate.

I. Photosensitive colored resin composition The photosensitive colored resin composition for a color filter according to the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The photoinitiator contains a compound represented by the following general formula (A).

［一般式（Ａ）中、Ｒ^１１は炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基である。Ｒ^１２は炭素数１〜１２の基である。Ｒ^１３は一般式（Ｂ）又は一般式（Ｃ）で表される基である。Ｙは硫黄原子又は酸素原子である。］

[In general formula (A), R < ¹¹ > is a C1-C5 alkyl group or a C1-C5 alkoxy group. R ¹² is a group having 1 to ¹² carbon atoms. R ¹³ is a group represented by the general formula (B) or the general formula (C). Y is a sulfur atom or an oxygen atom. ]

［一般式（Ｂ）及び一般式（Ｃ）において、Ｚは酸素原子、硫黄原子又は−Ｎ（Ｒ_ｚ）−（Ｒ_ｚは水素原子又は炭素数１〜５のアルキル基）であり、一般式（Ｂ）及び一般式（Ｃ）において各水素原子は置換されていてもよい。］

[In General Formula (B) and General Formula (C), Z is an oxygen atom, a sulfur atom, or -N (R _z )-(R _z is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); Each hydrogen atom in (B) and general formula (C) may be substituted. ]

  The photosensitive colored resin composition for a color filter according to the present invention has excellent curability and high residual film rate by using the compound represented by the general formula (A) as a photoinitiator. It is possible to produce a colored resin composition. In particular, for example, when the coloring material concentration is high, the integrated exposure amount is small, etc., it was difficult to prepare a colored resin composition having excellent curability and a high residual film rate by the conventional technique, Even in such a case, the photosensitive colored resin composition for a color filter according to the present invention has excellent curability and can be manufactured into a photosensitive colored resin composition having a high residual film rate.

The effect of exhibiting the above-mentioned effects by using the compound represented by the general formula (A) as a photoinitiator has not been elucidated but is presumed as follows.
First, in the compound represented by the general formula (A) used in the present invention, since the R ¹¹ site is an alkyl group such as a methyl group or the like, radicals can be efficiently added to the amount of the photoinitiator added. Can occur. Therefore, it is presumed that excellent curability is obtained and the residual film rate is improved even if the coloring material concentration in the colored resin composition is increased or the integrated exposure amount is small.
Furthermore, according to the photosensitive colored resin composition of the present invention, since excellent curability is obtained, the components such as dyes and pigments in the cured product are confined, and thus during the production of the color filter or in the display device. It was also found that the exudation of these components during driving was suppressed and the reliability of the color filter was improved.

The photosensitive colored resin composition for a color filter of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and does not impair the effects of the present invention. Within the range, other components may be further contained.
Hereinafter, each component of the color material dispersion of the present invention will be described in detail in order from the photoinitiator characteristic of the present invention.

[Photoinitiator]
<Compound represented by formula (A)>
The photoinitiator used in the present invention contains a compound represented by the following general formula (A).

［一般式（Ａ）中、Ｒ^１１は炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基である。Ｒ^１２は炭素数１〜１２の基である。Ｒ^１３は一般式（Ｂ）又は一般式（Ｃ）で表される基である。Ｙは硫黄原子又は酸素原子である。］

[In general formula (A), R < ¹¹ > is a C1-C5 alkyl group or a C1-C5 alkoxy group. R ¹² is a group having 1 to ¹² carbon atoms. R ¹³ is a group represented by the general formula (B) or the general formula (C). Y is a sulfur atom or an oxygen atom. ]

［一般式（Ｂ）及び一般式（Ｃ）において、Ｚは酸素原子、硫黄原子又は−Ｎ（Ｒ_ｚ）−（Ｒ_ｚは水素原子又は炭素数１〜５のアルキル基）であり、一般式（Ｂ）及び一般式（Ｃ）において各水素原子は置換されていてもよい。］

[In General Formula (B) and General Formula (C), Z is an oxygen atom, a sulfur atom, or -N (R _z )-(R _z is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); Each hydrogen atom in (B) and general formula (C) may be substituted. ]

Well-known oxime ester-based photoinitiators are those containing a carbazole group. The oxime ester photoinitiator containing a carbazole group tends to exhibit a yellow color, which causes a decrease in the brightness of green and blue.
Since the oxime ester photoinitiator represented by the general formula (A) does not contain a carbazole group, it has high transparency and high green and blue brightness.

Since the R ¹³ site of the oxime ester-based photoinitiator represented by the general formula (A) contains a condensed ring of a 5-membered ring and a 6-membered ring, the conjugated system is extended, so that the light receiving range is widened and the sensitivity is increased. Is improved. Moreover, since the excitation efficiency (quantum efficiency) is increased, it is presumed that the sensitivity is improved.

Further, in the oxime ester-based photoinitiator represented by the general formula (A), the R ¹¹ site is an alkyl group such as a methyl group, etc., radical migration is faster than in the case of a phenyl group, and the sensitivity is improved. To do.

The alkyl group or alkoxy group of R ¹¹ preferably has 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms, from the viewpoint of radical migration rate.

R ¹² has 1 to 12 carbon atoms, and specific examples thereof include an alkyl group, an aryl group, and a cycloalkyl group. Further, the ends of the alkyl group, aryl group and cycloalkyl group may be substituted with halogen (F, Cl, Br, I).
The alkyl group may be linear or branched, but is preferably branched.

R ¹³ is a group represented by the general formula (B) or the general formula (C), and specifically, a benzofuranyl group, a benzothienyl group, an indole group, or each hydrogen atom in these groups is substituted with a substituent. The ones that have been done are listed.
Specific examples of the substituent include an alkyl group having 1 to 10 carbon atoms (which may be linear or branched), an alkoxy group having 1 to 10 carbon atoms (which may be linear or branched). May be used), an aryl group, an amino group, a nitro group and the like.
Further, in the group represented by the general formula (B) or the general formula (C), a plurality of hydrogen atoms may be substituted with a substituent.

  Y is a sulfur atom or an oxygen atom, and preferably a sulfur atom.

  Specific examples of the compound represented by the general formula (A) include compounds described in Synthesis Examples 1 and 2 described below, and some compounds described in International Publication No. 2015/036910.

  The compound represented by the general formula (A) may be used in 100 parts by mass in 100 parts by mass of the photoinitiator used in the photosensitive colored resin composition of the present invention. You may use it in combination with the other photoinitiator different from the compound represented by. The photoinitiator used in the photosensitive colored resin composition of the present invention includes a chain transfer agent in addition to the photopolymerization initiator.

<Other photoinitiators>
Examples of the other photoinitiator include a dioxime ester-based photoinitiator containing two oxime ester groups in the molecule and one oxime ester group in the molecule different from the compound represented by the general formula (A). Examples include oxime ester photoinitiators, α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents.
Among them, when forming a fine line pattern, the linearity is further improved, and the ability to form a fine line pattern as designed for the mask line width is improved. It is preferable to use at least one of an aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent in combination.

The α-aminoketone-based photoinitiator has a property of curing the middle part from the surface of the coating film and easily suppresses the deep-layer curability of the coating film. It is preferable because it has a high tendency to improve the deep-part curability.
Examples of the α-aminoketone-based photoinitiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (eg, Irgacure 907, manufactured by BASF), 2-benzyl-2- (Dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ 4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 379EG, manufactured by BASF) and the like can be mentioned.
The α-aminoketone-based photoinitiator may be used alone or in combination of two or more, and among them, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and, It is preferable to use 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone in combination from the viewpoint of improving the residual film rate.

The biimidazole-based photoinitiator has a property of curing the coating film deep portion, and easily suppresses the coating film surface curability, and when combined with the compound represented by the general formula (A), the coating film surface curability is improved. It is preferable because it tends to be improved.
Examples of the biimidazole-based photoinitiator include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) ) -4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl- 1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1 2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 , 4,6-Tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like.
The biimidazole photoinitiator may be used alone or in combination of two or more, and among them, it is preferable to use a thiol chain transfer agent from the viewpoint of improving the curability of the coating film.
Further, it is preferable to use the compound represented by the general formula (A) in combination with a biimidazole-based photoinitiator and the α-aminoketone-based photoinitiator, because the residual film rate and the linearity are improved. .
The phrase "improved linearity" means that the colored layer formed in the developing step after applying the coloring composition has less irregularities at the end and is formed in a linear shape.

Examples of the thioxanthone photoinitiator include 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2,4-dichlorothioxanthone.
The thioxanthone-based photoinitiator may be used alone or in combination of two or more, and among them, 2,4-isopropylthioxanthone and 2,4-diethylthioxanthone are preferably used because the transfer of radical generation is improved. preferable.
In addition, it is preferable to use the compound represented by the general formula (A) in combination with a thioxanthone photoinitiator and the α-aminoketone photoinitiator, because the residual film rate is improved.

Although the acylphosphine oxide-based photoinitiator has a property of causing less yellowing due to heat, it generally has low sensitivity and may not have sufficient curability, but is represented by the general formula (A). It is preferable to combine the compound with the compound described above because of the high tendency to improve the overall curability of the coating film.
Examples of the acylphosphine oxide photoinitiator include benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, and 3, 4-dimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 , 4,4-trimethyl-pentylphosphine oxide, bis (2,6-dimethylbenzoyl) -ethylphosphine oxide and the like.
The acylphosphine oxide-based photoinitiator may be used alone or in combination of two or more kinds. Among them, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferably used as a coating film curability. Is preferable because it improves

The mercapto-based chain transfer agent has a property of receiving radicals from a slow-reacting radical and accelerating the reaction, and is particularly preferable in combination with a biimidazole-based photoinitiator since it tends to improve the reaction rate.
Examples of the mercapto chain transfer agent include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, and 3-mercaptobenzothiazole. Mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3- Mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) Rate), pen Erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) and the like.
As the mercapto chain transfer agent, one may be used alone or two or more may be used in combination, and among them, 2-mercaptobenzothiazole is preferably used from the viewpoint of improving the reaction rate.

The total content of photoinitiators used in the color filter photosensitive colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, but the solid content of the color filter photosensitive colored resin composition It is preferably 0.1% by mass or more and 12.0% by mass or less, and more preferably 1.0% by mass or more and 8.0% by mass or less with respect to the total amount. When the content is more than the above lower limit, photocuring proceeds sufficiently, and the exposed portion is less likely to be eluted during development. On the other hand, when the amount is less than the above upper limit, the developing time can be sufficiently shortened to improve the productivity, and the desired pattern can be easily obtained without increasing the line width too much.
In addition, the solid content is everything except a solvent, and includes a liquid polyfunctional monomer and the like.

  The content of the compound represented by the general formula (A) used in the photosensitive colored resin composition for a color filter of the present invention is preferably, based on the total solid content of the photosensitive colored resin composition for a color filter. It is in the range of 0.1% by mass or more and 8.0% by mass or less, more preferably 0.5% by mass or more and 6.0% by mass or less. When the content is more than the above lower limit, photocuring proceeds sufficiently, and the exposed portion is less likely to elute during development. On the other hand, when the amount is less than the above upper limit, the developing time can be sufficiently shortened to improve the productivity, and the desired pattern can be easily obtained without increasing the line width too much.

When the compound represented by the general formula (A) and the other photoinitiator are used in combination as the photoinitiator used in the present invention, the content of the compound represented by the general formula (A) is Is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and more preferably 20 parts by mass or more in 100 parts by mass in total of the photoinitiator used in the photosensitive colored resin composition of the present invention. Is more preferable, and more preferably 30 parts by mass or more.
On the other hand, the content of the compound represented by the general formula (A) depends on the amount of the light used in the photosensitive colored resin composition of the present invention from the viewpoint of sufficiently exerting the combined effect with the other photoinitiator. The amount is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less, based on 100 parts by mass of the total amount of the initiator.

  As the photoinitiator used in the present invention, further selected from α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents. In the case of containing at least one of the above, the total content thereof is preferably 0.4% by mass or more and 4.0% by mass or less, more preferably based on the total solid content of the photosensitive colored resin composition for a color filter. Is in the range of 0.5 mass% or more and 2.0 mass% or less.

  When the compound represented by the general formula (A) is combined with an α-aminoketone photoinitiator and a biimidazole photoinitiator and / or a thioxanthone photoinitiator as the photoinitiator used in the present invention. The ratio of the α-aminoketone photoinitiator to the biimidazole photoinitiator and / or the thioxanthone photoinitiator is 100 parts by mass of the α-aminoketone photoinitiator. The amount of the thioxanthone-based photoinitiator is preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 10 parts by mass or more and 40 parts by mass or less from the viewpoint of achieving both coating film curability and pattern shape.

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

C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and C.I. I. Pigment Yellow 150 derivative pigment;
C. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 06,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Pigment Green 7, 36, 58, 59;
C. I. Pigment Brown 23, 25;
C. I. Pigment Black 1, 7.

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

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

As the dispersible dye, a dye (lake pigment) which has become dispersible by being insolubilized in a solvent by imparting various substituents to the dye or using a known lake formation (chlorination) method, and solubility A dye which can be dispersed by using in combination with a solvent having a low solvent is mentioned. By using such a dispersible dye in combination with the dispersant, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes and phthalocyanine dyes.
Among these, xanthene dyes are preferable because of their high heat resistance. As the xanthene-based acid dye, it is preferable to have a compound represented by the following general formula (III), that is, a rhodamine-based acid dye.

［一般式（ＩＩＩ）中、Ｒ^Ｉ〜Ｒ^ＩＶ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^ＩとＲ^ＩＩＩ、Ｒ^ＩＩとＲ^ＩＶが結合して環構造を形成してもよい。Ｒ^Ｖ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（ＩＩＩ）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 the general formula (III), R ^{I to} R ^IV each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R ^I and R ^III are bonded to each other, and R ^II and R ^IV are bonded to each other. You may form a ring structure. R ^V represents an acidic group, and X represents a halogen atom. m represents an integer of 0 to 5. The general formula (III) has one or more acidic groups, and n is an integer of 0 or more. ]

The alkyl group in R ^{I to} R ^IV is not particularly limited. Examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and 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 and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group and the like. May have a halogen atom or an acidic group.
The aryl group in R ^{I to} R ^IV is not particularly limited. For example, an aryl group having 6 to 20 carbon atoms which may have a substituent is mentioned, and among them, a group having a phenyl group, a naphthyl group, or the like is preferable. Examples of the heteroaryl group for R ^{I to} R ^IV include a heteroaryl group which may have a substituent having 5 to 20 carbon atoms, and a hetero atom preferably contains a nitrogen atom, an oxygen atom, or a sulfur atom. .
Examples of the substituent that the aryl group or the 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, a carboxylic acid ester group and the like. .
Note that R ^{I to} R ^IV may be the same or different.

Specific examples of the acidic group or a salt thereof, a carboxyl group (-COOH), a carboxylato group (-COO ^-), carboxylate (. -COOM, where M is a metal atom), a sulfonato group (-SO 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 sulfonate group (—SO ₃ M). Examples of the metal atom M include sodium atom and potassium atom.

As the compound represented by the general formula (III), Acid Red 50, Acid Red 52, Acid Red 289, Acid Violet 9, Acid Violet 30, Acid Blue 19 and the like are preferable from the viewpoint of high brightness.
From the viewpoint of heat resistance, a compound having a betaine structure in which m = 1 and n = 0 in the general formula (III) is preferable.
In addition, among them, m = 1 and n = 0, R ^I and R ^II are each independently an alkyl group or an aryl group, and R ^III and R ^IV are each independently an aryl group or a heteroaryl group. It is preferable that the colored layer having excellent brightness and light resistance can be formed.
The method for producing the compound represented by the general formula (III) is not particularly limited, but can be obtained, for example, with reference to JP-A-2010-212198.

In the metal lake color material of the xanthene-based acid dye, one containing a metal atom is used as a lake agent. The heat resistance of the coloring material is increased by using the laking agent containing a metal atom. As such a laking agent, a laking agent containing a metal atom which becomes a divalent or higher valent metal cation is preferable.
As a guide, if the amount of the dye dissolved in 10 g of the solvent (or mixed solvent) is 100 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

The average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as it can produce a desired color when used as a colored layer of a color filter, and it varies depending on the type of coloring material used. Is preferably in the range of 10 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, it is possible to make a display device having a color filter manufactured using the color material dispersion liquid of the present invention have high contrast and high quality. it can.
The average primary particle diameter of the coloring material in the present invention represents the “volume distribution median diameter (D50)”. The average primary particle size of the coloring material is a scanning transmission electron by attaching a dedicated bright-field STEM sample stand and an optional detector to a field emission scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation. It can be used as a microscope (hereinafter abbreviated as "STEM"), takes a 200,000 times STEM photograph, imports it into the software below, and arbitrarily selects 100 coloring materials on the photograph, each diameter (transmission length) Is measured and determined as a 50% cumulative particle size by volume from a volume-based distribution.

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

  The total content of the color materials may be 3% by mass to 65% by mass, more preferably 4% by mass to 60% by mass, based on the total solid content of the photosensitive colored resin composition for a color filter. preferable. When it is at least the above lower limit, the colored layer has a sufficient color density when the photosensitive colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm). Further, when it is at most the above upper limit value, it is possible to obtain a colored layer which is excellent in storage stability and has sufficient hardness and adhesion to a substrate. In particular, when forming a coloring layer having a high coloring material concentration, the total content of coloring materials is 15% by mass to 65% by mass, more preferably based on the total solid content of the photosensitive colored resin composition for color filters. Is preferably blended at a ratio of 25% by mass to 60% by mass.

[Alkali-soluble resin]
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those which act as a binder resin and are soluble in an alkali developing solution 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.
The preferred alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group, and specifically, an acrylic copolymer having a carboxy group and a styrene-acrylic copolymer having a carboxy group. Examples thereof include a system resin and an epoxy (meth) acrylate resin having a carboxy group. Particularly preferred among these are those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Further, two or more kinds of acrylic resins such as acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be mixed and used.

Acrylic resins such as acrylic copolymers having a structural unit having a carboxyl group, and styrene-acrylic copolymers having a carboxyl group include, for example, a carboxyl group-containing ethylenically unsaturated monomer, and optionally a copolymer. It is a (co) polymer obtained by (co) polymerizing another polymerizable monomer 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. Be done. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, or citraconic anhydride may be used as the precursor of the carboxyl group. Among them, (meth) acrylic acid is particularly preferable in terms 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 which is a bulky group in the alkali-soluble resin, shrinkage at the time of curing is suppressed, peeling from the substrate is mitigated, and substrate adhesion is improved. Moreover, 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 has not been clarified, the inclusion of a bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in higher strength of the coating film and suppression of swelling by the solvent. Presumed to be one.
Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination thereof. May have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group and an amide group. Above all, when the aliphatic ring is contained, the heat resistance and the adhesion of the colored layer are improved, and the brightness of the obtained colored layer is improved.
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 rings such as benzene, naphthalene, anthracene, phenanthrene, fluorene; chain polycycles such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, and cardo structures represented by the following chemical formula (5) Be done.

When the hydrocarbon ring contains an aliphatic ring, it is preferable because the heat resistance and adhesion of the colored layer are improved and the brightness of the obtained colored layer is improved.
In addition, when the cardo structure represented by the chemical formula (5) is included, the curability of the colored layer is improved, and the solvent resistance (suppression of NMP swelling) is particularly preferable.

In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each structural unit by using an acrylic copolymer having a structural unit having a hydrocarbon ring, in addition to the structural unit having a carboxyl group. It is preferable because the amount of the structural unit having a hydrocarbon ring can be increased to easily improve the function of the structural unit.
The acrylic copolymer having a constitutional unit having a carboxyl and the above hydrocarbon ring should be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". You can
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring combined with the compound represented by the general formula (A) include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl ( Examples thereof include (meth) acrylate, phenoxyethyl (meth) acrylate, and styrene. Cyclohexyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylate, adamantyl (meth) acrylate, and styrene are preferable.

The alkali-soluble resin used in the present invention also preferably has an ethylenic double bond in the side chain. When the resin composition has an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond in the curing step of the resin composition during the production of the color filter. By combining with the compound represented by the above general formula (A) used in the present invention, the film strength of the cured film is further improved and the development resistance is improved, and the thermal shrinkage of the cured film is suppressed, so that the substrate Will be excellent in adhesion.
The method for introducing the ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, is added to the carboxyl group of the alkali-soluble resin, and an ethylenic double bond is introduced into the side chain. Alternatively, a method of introducing a structural unit having a hydroxyl group into the 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. And so on.

  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 color filters, but also functions as a component that improves solubility in a solvent and further resolubility in a solvent.

  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 amount of each constituent unit charged.

The amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total amount of the monomers, from the viewpoint of obtaining a good pattern. On the other hand, the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, and preferably 40% by mass or less, from the viewpoint of suppressing film roughness on the pattern surface after development. More preferably.
If the proportion of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the resulting coating film in an alkali developing solution is lowered, which may impair the effects of the present invention. Further, when the proportion of the carboxyl group-containing ethylenically unsaturated monomer exceeds 50% by mass, the formed pattern tends to come off from the substrate and the pattern surface may become rough during development with an alkali developing solution.

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

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

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

As the alkali-soluble resin, it is preferable to select and use one having an acid value of 50 mgKOH / g or more from the viewpoint of developability (solubility) in an alkaline aqueous solution used for the developing solution. 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 alkaline aqueous solution used for a developer and adhesion to a substrate. It is preferably 70 mgKOH / g or more and 280 mgKOH / g or less.
In the present invention, the acid value can be measured according to JIS K0070.

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is determined by combining the compound represented by the general formula (A) used in the present invention with the film strength of the cured film. From the standpoint of obtaining the effects of improved image development resistance, improved development resistance, and excellent adhesion to the substrate, the range of 100 to 2000 is preferable, and the range of 140 to 1500 is particularly preferable. When the ethylenically unsaturated bond equivalent is 2000 or less, development resistance and adhesion are excellent. Further, when it is 100 or more, the ratio of the constitutional unit having the carboxy group and the other constitutional units such as the constitutional unit having a hydrocarbon ring can be relatively increased, and therefore the developability and the heat resistance are excellent. There is. It is preferable to use the compound represented by the general formula (A) used in the present invention in combination with the above-mentioned content.
Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per 1 mol of ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following mathematical formula (1).

Formula (1)
Ethylenically unsaturated bond equivalent (g / mol) = (W (g)) / (M (mol))
(In the 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 by measuring the number of ethylenic double bonds contained in 1 g of the 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 photosensitive colored resin composition for a color filter may be used alone or in combination of two or more, and the content thereof is not particularly limited. The alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass, based on the total solid content of the photosensitive colored resin composition for filters. When the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained, and when the content of the alkali-soluble resin is more than the above upper limit, the film may be rough during development or The pattern may be chipped.

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

  These polyfunctional (meth) acrylates may be used alone or in combination of two or more. Further, when the photo-curable resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Those having the above are preferable, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate and pentaerythritol triacrylate are preferable. (Meth) acrylate, succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) ) Succinic acid modified acrylate, dipen Hexa (meth) acrylate are preferable.

The content of the polyfunctional monomer used in the color filter photosensitive colored resin composition is not particularly limited, but the polyfunctional monomer is preferably 5 relative to the total solid content of the color filter photosensitive colored resin composition. It is in the range of 10% by mass to 60% by mass, more preferably 10% by mass to 40% by mass. If the content of the polyfunctional monomer is less than the above lower limit, the photo-curing does not proceed sufficiently and the exposed part may elute during development. May decrease.
The content of the polyfunctional monomer used in the photosensitive colored resin composition for a color filter and the content of the compound represented by the general formula (A) are excellent in curability and residual film rate. From the viewpoint of improving electrical reliability, the amount of the compound represented by the general formula (A) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, based on 100 parts by mass of the polyfunctional monomer. The amount is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.

[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 photosensitive colored resin composition and can dissolve or disperse them. The solvent can be used alone or in combination of two or more kinds.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester-based solvents such as ethyl lactate and cyclohexanol acetate; such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone Ton-based solvent; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, glycol ether acetate-based solvent such as ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxy Carbitol acetate solvents such as ethoxyethyl acetate and butyl carbitol acetate (BCA); 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, diethyl Glycol ether solvents such as glycol diethyl ether, propylene glycol monomethyl ether and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; γ-butyrolactone etc. Lactone solvent; cyclic ether solvent such as tetrahydrofuran; unsaturated hydrocarbon solvent such as benzene, toluene, xylene, naphthalene; saturated hydrocarbon solvent such as N-heptane, N-hexane, N-octane; toluene, Examples include organic solvents such as aromatic hydrocarbons such as xylene. Among these solvents, glycol ether acetate-based solvent, carbitol acetate-based solvent, glycol ether-based solvent and ester-based solvent are preferably used from the viewpoint of solubility of other components. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, Also, it is preferable that it is at least one selected from the group consisting of 3-methoxybutyl acetate from the viewpoint of solubility of other components and coating suitability.

  In the photosensitive colored resin composition according to the present invention, the content of the solvent may be appropriately set within a range in which the colored layer can be accurately formed. Usually, it is preferably in the range of 55% by mass to 95% by mass, and more preferably in the range of 65% by mass to 88% by mass with respect to the total amount of the photosensitive colored resin composition for a color filter containing the solvent. More preferably. When the content of the solvent is within the above range, the coatability can be excellent.

[Dispersant]
In the photosensitive colored resin composition of the present invention, it is preferable that the coloring material is used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine-based surface active agents can be used. Among the surfactants, the polymer dispersant is preferable because it can be dispersed uniformly and finely.

  Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; (Partial) ammonium salt and (partial) alkylamine salt; (Co) polymer of hydroxyl group-containing unsaturated carboxylic acid ester such as hydroxyl group-containing polyacrylic acid ester and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxane Long-chain polyaminoamide phosphates; Polyethyleneimine derivatives (amides obtained by reacting poly (lower alkyleneimine) with polyester containing free carboxyl group and their bases); Polyallylamine derivatives (polyallylamine and free carboxyl) -Condensation of amides with group-containing polyesters, polyamides or esters The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.

As the polymer dispersant, among others, a polymer dispersant having a amine value, which contains a nitrogen atom in the main chain or a side chain, can be preferably dispersed in the colorant and has good dispersion stability. Among them, a polymer dispersant made of a polymer containing a repeating unit having a tertiary amine is preferable from the viewpoints of good dispersibility, no precipitation of foreign matter during coating film formation, and improvement of brightness and contrast.
The repeating unit having a tertiary amine is a site having an affinity with the coloring material. The polymer dispersant composed of a polymer containing a repeating unit having a tertiary amine usually contains a repeating unit serving as a site having an affinity with a solvent. As a polymer containing a repeating unit having a tertiary amine, among others, a block copolymer having a block portion composed of a repeating unit having a tertiary amine and a block portion having a solvent affinity is heat resistant. It is preferable in that it is possible to form a coating film having excellent brightness and high brightness.

The repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the block polymer or may constitute the main chain.
Among them, a repeating unit having a tertiary amine in the side chain is preferable, and in particular, from the viewpoint that the main chain skeleton is difficult to thermally decompose and the heat resistance is high, the structure is represented by the following general formula (I). Are more preferable.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基、Ｑは、直接結合又は２価の連結基、Ｒ^２は、炭素数１〜８のアルキレン基、−［ＣＨ（Ｒ^５）−ＣＨ（Ｒ^６）−Ｏ］_ｘ−ＣＨ（Ｒ^５）−ＣＨ（Ｒ^６）−又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−（ＣＨ_２）_ｙ−で示される２価の有機基、Ｒ^３及びＲ^４は、それぞれ独立に、置換されていてもよい鎖状又は環状の炭化水素基を表すか、Ｒ^３及びＲ^４が互いに結合して環状構造を形成する。Ｒ^５及びＲ^６は、それぞれ独立に水素原子又はメチル基である。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms, and- [CH (R ⁵ ). _{^{-CH (R 6) -O] x}} -CH (R 5) -CH (R 6) - or _{- [(CH 2) y -O} ] z - (CH 2) y - 2 monovalent organic group represented by , R ³ and R ⁴ each independently represent a optionally substituted linear or cyclic hydrocarbon group, R ³ and R ⁴ form a ring structure by bonding with each other .R ⁵ and R Each of ⁶ is independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

  Examples of the divalent linking group Q in the general formula (I) include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (- R'-OR "-: R'and R" are each independently an alkylene group) or a combination thereof. Among them, Q is —COO— group or —CONH— from the viewpoint of heat resistance of the obtained polymer, solubility in propylene glycol monomethyl ether acetate (PGMEA) which is preferably used as a solvent, and a relatively inexpensive material. It is preferably a group.

Divalent organic group ^{R 2} in the general formula (I) is an alkylene group having 1 to 8 carbon ^{atoms, - [CH (R 5)} -CH (R 6) -O] x -CH (R 5) -CH ^{(R 6)} - or _{- [(CH 2) y -O} ] z - (CH 2) y - is. The alkylene group having 1 to 8 carbon atoms may be linear or branched, and examples thereof include methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, and various hexylene groups. And various octylene groups.
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.
As the R ^2, from the viewpoint of dispersibility, preferably an alkylene group having 1 to 8 carbon atoms, among them, R ² is a methylene group, an ethylene group, a propylene group, more preferably a butylene group, a methylene group and ethylene More preferred are groups.

Examples of the cyclic structure formed by R ³ and R ⁴ of the general formula (I) bonded to each other include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. To be The nitrogen-containing heterocycle preferably has no aromaticity, and is more preferably a saturated ring.

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

  In the block part composed of the repeating unit having a tertiary amine, it is preferable that the structural unit represented by the general formula (I) is contained in three or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferably 3 to 100, more preferably 3 to 50, and further preferably 3 to 30.

A block having a block portion (hereinafter sometimes referred to as A block) composed of a repeating unit having a tertiary amine and a block portion having solvent affinity (hereinafter sometimes referred to as B block). The block portion having a solvent affinity in the polymer does not have a constitutional unit represented by the general formula (I) from the viewpoint of improving the solvent affinity and improving the dispersibility, and the general formula (I It has a solvent-affinity block part having a structural unit copolymerizable with I). In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and may be, for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer or the like. Among them, the AB block copolymer or the ABA block copolymer is preferable because of its excellent dispersibility.
The structural unit copolymerizable with the general formula (I) is a structural unit represented by the following general formula (II) from the viewpoint of improving heat resistance while improving dispersibility and dispersion stability of the coloring material. Is preferred.

（一般式（ＩＩ）中、Ｒ^７は、水素原子又はメチル基、Ａは、直接結合又は２価の連結基、Ｒ^８は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−［ＣＨ（Ｒ^９）−ＣＨ（Ｒ^１０）−Ｏ］_ｘ−Ｒ^１１又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^１１で示される１価の基である。Ｒ^９及びＲ^１０は、それぞれ独立に水素原子又はメチル基であり、Ｒ^１１は、水素原子、あるいは炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アラルキル基、アリール基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^１２で示される１価の基であり、Ｒ^１２は水素原子又は炭素数１〜５の直鎖状、分岐状、又は環状のアルキル基である。ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In the general formula (II), R ⁷ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, R ⁸ is an alkyl group having 1 to 18 carbon atoms, and an alkenyl having 2 to 18 carbon atoms. group, an aralkyl group, an aryl ^{group, - [CH (R 9)} -CH (R 10) -O] x -R 11 or _- a monovalent group represented by _{[(CH 2) y -O]} z -R 11 R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, aryl group, _-CHO, a monovalent group represented by -CH 2 CHO, or _-CH 2 COOR ^{12, R 12} is a hydrogen atom or a number from 1 to 5 straight, branched, or cyclic alkyl X is an integer of 1 to 18, y is an integer of 1 to 5, z Represents an integer of 1 to 18.)

  The divalent linking group A in the above general formula (II) may be the same as Q in the above general formula (I), and propylene glycol preferably used as the heat resistance or solvent of the obtained polymer. A is preferably a —COO— group because of its solubility in monomethyl ether acetate (PGMEA) and its relatively inexpensive material.

In R ⁸ , the alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, Examples thereof include a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group, various butenyl groups, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecenyl groups, Examples thereof include a cyclopentenyl group, a cyclohexenyl group and a cyclooctenyl group.
Among them, R ⁸ is preferably a methyl group, various butyl groups, various hexyl groups, benzyl group, cyclohexyl group and hydroxyethyl group from the viewpoints of dispersibility and substrate adhesion.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group and a xylyl group. The aryl group preferably has 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group and a biphenylmethyl group. The carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 14.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group and a halogen atom.

Further, R ¹¹ is a hydrogen atom or may have a substituent, and has an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO. , Or a monovalent group represented by —CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms.
In the monovalent group represented by R ¹¹ , the substituent which may be possessed is, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a halogen atom such as F, Cl or Br. And so on.
Alkyl group, and alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group having 1 to 18 carbon atoms of the above ^{R 11} is as shown by the ^{R 8.}
In the above R ⁸ , x, y and z are the same as R ² in the general formula (I).

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

  The number of structural units forming the solvent-affinitive block portion may be appropriately adjusted within the range in which the dispersibility of the coloring material is improved. Among them, the number of constitutional units constituting the solvent affinity block part is 10 to 200 from the viewpoint that the solvent affinity part and the coloring material affinity part act effectively and improve the dispersibility of the coloring material. It is preferably 10 to 100, more preferably 10 to 70.

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 of may be included.
In the block copolymer used as the dispersant of the present invention, the ratio of the number of units m of the structural unit represented by the general formula (I) to the number n of other structural units constituting the block portion having solvent affinity. The m / n is preferably in the range of 0.01 to 1, and more preferably in the range of 0.05 to 0.7 from the viewpoint of dispersibility and dispersion stability of the coloring material.

Further, among them, in the present invention, the dispersant is a polymer having a structure represented by the general formula (II) and an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less. It is preferable in terms of improving the brightness and contrast without depositing foreign matter.
When the amine value is within the above range, the viscosity stability with time and the heat resistance are excellent, and the alkali developability and the solvent resolubility are also excellent. In the present invention, the amine value of the dispersant is preferably 80 mgKOH / g or more, and more preferably 90 mgKOH / g or more, from the viewpoints of dispersibility and dispersion stability. On the other hand, the amine value of the dispersant is preferably 110 mgKOH / g or less, more preferably 105 mgKOH / g or less, from the viewpoint of solvent re-solubility.
The amine value is the mg number of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by the 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 the block copolymer itself used as the dispersant The amine value of can be measured.

The lower limit of the acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more from the viewpoint of the effect of suppressing development residues. Among them, the acid value of the dispersant is more preferably 2 mgKOH / g or more from the viewpoint that the effect of suppressing the development residue is more excellent. 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 that deterioration of development adhesion and deterioration of solvent resolubility can be prevented. preferable. Among them, the acid value of the dispersant is more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, from the viewpoint of good development adhesion and solvent resolubility.
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, more preferably 2 mgKOH / g or more. This is because the effect of suppressing the development residue is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH / g or less, more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less. . This is because the development adhesiveness and the solvent re-solubility are improved.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C. or higher from the viewpoint of improving the development adhesion. That is, whether the dispersant is a block copolymer before salt formation or a salt-type block copolymer, the glass transition temperature thereof is preferably 30 ° C. or higher. When the glass transition temperature of the dispersant is low, the temperature may be particularly close to the temperature of the developing solution (usually about 23 ° C.) and the developing adhesion may be lowered. This is presumed to be because when the glass transition temperature is close to the temperature of the developing solution, the dispersant has a large movement during development, and as a result, the development adhesion is deteriorated. When the glass transition temperature is 30 ° C. or higher, the molecular movement of the dispersant during development is suppressed, and thus it is presumed that the decrease in development adhesion is suppressed.
The glass transition temperature of the dispersant is preferably 32 ° C. or higher, and 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 precise weighing.
The glass transition temperature of the dispersant in the invention can be determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

  When the concentration of the coloring material is increased and the content of the dispersant is increased, the amount of the binder is relatively decreased, so that the colored layer is easily separated from the base substrate during the development. When the dispersant contains a B block containing a constitutional unit derived from a carboxy group-containing monomer and has the above-mentioned specific acid value and glass transition temperature, development adhesion is improved. If the acid value is too high, the developability is excellent, but the polarity is too high, and it is presumed that peeling tends to occur on the contrary during development.

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

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

In the block copolymer 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 falls within the specific acid value range, and particularly Although not limited, it is preferably 0.05% by mass to 4.5% by mass, and 0.07% by mass to 3.7% by mass, based on the total mass of all the structural units of the block copolymer. Is more preferable.
The content ratio of the constitutional unit derived from a carboxy group-containing monomer is not less than the lower limit, the development residue suppressing effect is expressed, and if the content is not more than the upper limit, deterioration of development adhesion and solvent resolubility It can prevent the deterioration.
The constituent unit derived from the carboxy group-containing monomer may have the above-mentioned specific acid value, and may be composed of one kind or may contain two or more kinds of constituent units.

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

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

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

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

  Specific examples of the block copolymer having such a block portion comprising a repeating unit having a tertiary amine and a block portion having a solvent affinity include, for example, the block copolymer described in Japanese Patent No. 4911253. It can be mentioned as a suitable one.

  When the color material is dispersed using the polymer containing the repeating unit having the tertiary amine as a dispersant, the polymer containing the repeating unit having the tertiary amine with respect to 100 parts by mass of the color material. Is preferably 15 parts by mass to 300 parts by mass, and more preferably 20 parts by mass to 250 parts by mass. Within the above range, the dispersibility and dispersion stability are excellent, and the effect of improving the contrast is high.

In the present invention, from the viewpoint of dispersibility and dispersion stability of the coloring material, at least a part of amino groups in the polymer containing the repeating unit having a tertiary amine, an organic acid compound and a halogenated hydrocarbon are included. It is also preferable to use as a dispersant those in which and form a salt (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 the dispersibility of the coloring material is It is also preferable 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 as preferable examples.
Further, the halogenated hydrocarbon is preferably at least one kind of allyl halide such as allyl bromide and benzyl chloride and aralkyl halide, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

  The content of the dispersant is not particularly limited as long as it can uniformly disperse the coloring material, for example, the total solid content of the color filter photosensitive colored resin composition. On the other hand, it can be used in an amount of 1% by mass to 40% by mass. Further, it is preferably added in an amount of 2% by mass to 30% by mass, and particularly preferably in an amount of 3% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition for a color filter. When it is at least the above lower limit value, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition for a color filter is excellent. Further, if it is at most the above upper limit, the developability will be good. Particularly when a colored layer having a high coloring material concentration is formed, the content of the dispersant is 2% by mass to 25% by mass, more preferably based on the total solid content of the photosensitive colored resin composition for a color filter. It is preferable to mix it in a ratio of 3% by mass to 20% by mass.

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

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

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

The ratio of the mass (P) of the coloring material used in the present invention to the mass (V) of the solid content other than the coloring material (hereinafter sometimes referred to as “P / V ratio”) is the color layer of the color filter. In that case, it is not particularly limited as long as desired color development is possible, but it is preferably within the range of 0.05 or more and 1.00 or less, and within the range of 0.10 or more and 0.80 or less. More preferably, it is more preferably 0.15 or more and 0.75 or less, and particularly preferably 0.20 or more and 0.70 or less. When the P / V ratio is within the above range, a colored resin composition capable of forming a colored layer capable of desired color development can be obtained, and further, the colored resin composition can be uniformly dispersed in the colored resin composition. it can.
The photosensitive colored resin composition of the present invention has excellent curability even when the colorant concentration is particularly high, and the residual film rate is high, so that the P / V ratio is in the range of 0.4 or more. The range can be set as high as possible, which can contribute to improvement in brightness and color reproducibility.

In particular, in the case of a red colored resin composition, the P / V ratio is preferably 0.50 or more, more preferably 0.60 or more, and even more preferably 0.10 or less from the viewpoint of desired color development. It is preferably 74 or more. Further, it is preferably 1.0 or less.
In addition, in the case of a green colored resin composition, the P / V ratio is preferably 0.46 or more, more preferably 0.56 or more, and still more preferably 0. It is preferably 68 or more. Further, it is preferably 1.0 or less.
Further, in the case of a blue colored resin composition, the P / V ratio is preferably 0.24 or more, more preferably 0.34 or more, and still more preferably from the viewpoint of desired color development. It is preferably 41 or more. Further, it is preferably 1.0 or less. When each is at least the above lower limit value, the color density of the photosensitive colored resin composition for a color filter can be increased, and the color filter pixel can have a higher color rendering and a lower film thickness. Further, if each is less than or equal to the upper limit value, it is possible to obtain a colored layer having excellent storage stability, sufficient hardness, and adhesion to a substrate.
Among them, the red-colored resin composition and the green-colored resin composition are often required to have a high ratio of the color material in the solid content of the composition due to the difference in the coloring power between the color and the color material required by the color filter. In particular, in the case of a green colored resin composition, it is often necessary to increase the proportion of the pigment in the solid content of the composition as compared with the colored resin compositions of other colors. Therefore, the photosensitive colored resin composition of the present invention is particularly effective when used in a red colored resin composition and a green colored resin composition.

<Method for producing photosensitive colored resin composition for color filter>
The method for producing a colored resin composition for a color filter of the present invention includes a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, and various additives optionally used. From the viewpoint of improving the contrast, it is preferable to use a method in which the coloring material is uniformly dispersed in the solvent with a dispersant, and it can be prepared by mixing using a known mixing means. .
As the method for preparing the resin composition, for example, (1) first, a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion liquid, and the dispersion liquid is mixed with an alkali-soluble resin and a light. A method of mixing a polymerizable compound, a photoinitiator, and various optional components used as desired; (2) a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator in a solvent. A method in which an agent and various optional components used at the same time are added and mixed at the same time; (3) A dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent are optionally used in a solvent. A method in which various additive components are added and mixed, and then a coloring material is added and dispersed; (4) A coloring material dispersion liquid is prepared by adding a coloring material, a dispersant, and an alkali-soluble resin to a solvent. The dispersion liquid, an alkali-soluble resin, a solvent, and And the like; and polymerizable compound, a photoinitiator, by adding various additive components optionally used, mixing method.
Among these methods, the above methods (1) and (4) are preferable from the viewpoint of effectively preventing aggregation of the coloring material and allowing uniform dispersion.

  The method for preparing the color material dispersion liquid can be appropriately selected and used from conventionally known dispersion methods. For example, (1) a dispersant is mixed with a solvent in advance and stirred to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt between the amino group of the dispersant and the organic acid compound. Let A method in which this is mixed with a coloring material and other components as necessary and dispersed using a known stirrer or disperser; (2) a dispersant is mixed with a solvent and stirred to prepare a dispersant solution, Next, a method of mixing a coloring material and, if necessary, an organic acid compound, and optionally other components, and dispersing using a known stirrer or disperser; (3) mixing a dispersant with a solvent, Stir, adjust the dispersant solution, then mix the coloring material and other components as necessary, and after using a known stirrer or disperser to prepare a dispersion liquid, if necessary, an organic acid compound And the like.

  Examples of the disperser for performing the dispersion treatment include a two-roll, three-roll, etc. roll mill, a ball mill, a ball mill such as a vibrating ball mill, a paint conditioner, a continuous disc type bead mill, a continuous annular bead mill, and the like. As a preferable dispersion condition of the bead mill, the bead diameter used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

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

II. Color filter The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is for the color filter according to the present invention. It has a colored layer made of a cured product of a photosensitive colored resin composition.

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

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

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

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

(Shading part)
The light-shielding portion in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light-shielding portion in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. The light-shielding portion may be a thin metal film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light shielding portion may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, etc. is there.

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

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

III. Display Device A display device according to the present invention is characterized by having 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, and examples thereof include a liquid crystal display device and an organic light emitting display device.

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

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

  As a method for forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After forming the liquid crystal layer by the above method, the enclosed liquid crystal can be aligned by gradually cooling the liquid crystal cell to room temperature.

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

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

The fact that the target compound was synthesized in the following synthesis examples was confirmed by ¹ H- and ¹³ C-NMR spectra measured using a nuclear magnetic resonance apparatus.

(Synthesis Example 1: Synthesis of compound A1 (photoinitiator))
9.31 g of diphenyl sulfide solution cooled to 0 ° C. was added to 7.36 g of aluminum chloride in 50 mL of dichloromethane. Then, 5.56 g of chloroacetyl chloride was added at 0 ° C., and the mixture was stirred at room temperature for 2 hours. To the reaction mixture was added 7.33 g aluminum chloride and 7.06 g 4-methylpentanoic acid chloride at 0 ° C. and the mixture was stirred overnight. After the reaction, the mixture was poured into ice water, and the organic layer was extracted with dichloromethane. The extract was dried over magnesium sulfide, concentrated, and the residue was purified by column chromatography to obtain 11.22 g of an intermediate compound (A1-1) having the following structure.

  1.08 g of the intermediate compound (A1-1) was dissolved in 30 mL of acetone, 1.11 g of potassium carbonate and 0.73 g of salicylaldehyde were added, and the mixture was heated under reflux for 3 hours and stirred. The reaction mixture was cooled to room temperature, acidified by adding water and adding hydrochloric acid. The precipitate was filtered with a filter and dried to obtain 1.07 g of an intermediate compound (A1-2) having the structure below.

  1.07 g of the intermediate compound (A1-2) was dissolved in 10 mL of ethyl acetate, 0.35 g of hydroxyammonium chloride and 5 mL of pyridine were added, and the mixture was heated under reflux for 3 hours and stirred. The reaction mixture was cooled to room temperature and poured into water, the organic layer was extracted with ethyl acetate and then dried over magnesium sulfate. After concentration, the residue was purified by column chromatography to obtain 302 mg of the intermediate compound (A1-3) having the following structure.

  302 mg of the intermediate compound (A1-3) was dissolved in 14 mL of ethyl acetate, 78.5 mg of acetyl chloride and 111 mg of triethylamine were added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. After concentration, the residue was purified by column chromatography to obtain 240 mg of compound A1 (photoinitiator) having the following structure.

(Synthesis Example 2: Synthesis of compound A2 (photoinitiator))
9.31 g of diphenyl sulfide solution cooled to 0 ° C. was added to 7.36 g of aluminum chloride in 50 mL of dichloromethane. Then, 5.56 g of chloroacetyl chloride was added at 0 ° C., and the mixture was stirred at room temperature for 2 hours. To the reaction mixture, 7.33 g aluminum chloride and 5.59 g n-butyryl chloride were added at 0 ° C. and the mixture was stirred overnight. After the reaction, the mixture was poured into ice water, and the organic layer was extracted with dichloromethane. The extract was dried over magnesium sulfide, concentrated, and the residue was purified by column chromatography to obtain 10.35 g of an intermediate compound (A2-1) having the following structure.

  1.0 g of the intermediate compound (A2-1) was dissolved in 30 mL of acetone, 1.11 g of potassium carbonate and 0.73 g of salicylaldehyde were added, and the mixture was heated under reflux for 3 hours and stirred. The reaction mixture was cooled to room temperature, acidified by adding water and adding hydrochloric acid. The precipitate was filtered with a filter and dried to obtain 1.0 g of an intermediate compound (A2-2) having the following structure.

  1.0 g of the intermediate compound (A2-2) was dissolved in 10 mL of ethyl acetate, 0.35 g of hydroxyammonium chloride and 5 mL of pyridine were added, and the mixture was heated under reflux for 3 hours and stirred. The reaction mixture was cooled to room temperature and poured into water, the organic layer was extracted with ethyl acetate and then dried over magnesium sulfate. After concentration, the residue was purified by column chromatography to obtain 283 mg of an intermediate compound (A2-3) having the structure below.

  283 mg of the intermediate compound (A2-3) was dissolved in 14 mL of ethyl acetate, 78.5 mg of acetyl chloride and 111 mg of triethylamine were added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. After concentration, the residue was purified by column chromatography to obtain 226 mg of compound A2 (photoinitiator) having the following structure.

(Synthesis Example 3: Production of Dispersant (Block Copolymer A))
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottom 4-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and nitrogen was sufficiently replaced. 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) 2.2 parts by mass, 2-hydroxyethyl methacrylate (HEMA) 18.7 parts by mass, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by mass, methacryl 13.7 parts by mass of n-butyl acidate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA) and 17.5 parts by mass of methyl methacrylate (MMA) were added dropwise using an addition funnel over 60 minutes. .. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to give a solution having a solid content 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 to deprotect the structural unit derived from EEMA to obtain a structural unit derived from methacrylic acid (MAA). The resulting block copolymer PGMEA solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain a block A containing a structural unit represented by the general formula (I) and a structural unit derived from a carboxy group-containing monomer. To obtain a block copolymer A containing B block having a hydrophilic property (acid value 8 mgKOH / g, Tg 38 ° C.). When the block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography), the weight average molecular weight Mw was 7730. The amine value was 95 mgKOH / g.

(Synthesis example 4: Synthesis 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 under a nitrogen stream. did. After the dropping was completed, 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 7,000.
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 were 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 by using GMA, and the solid content is 42.6 mass. %, The acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000. The weight average molecular weight was measured by using a polystyrene as a standard substance and THF as an eluent by a Shodex GPC System-21H. The method for measuring the acid value was measured according to JIS K0070.

(Synthesis Example 5: Synthesis of alkali-soluble resin B solution)
An alkali-soluble resin B solution was obtained in the same manner as in Synthesis Example 4, except that 40 parts by mass of cyclohexyl methacrylate was used instead of BzMA in Synthesis Example 4. The solid content was 40% by mass, the acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

(Synthesis Example 6: Synthesis of alkali-soluble resin C solution)
An alkali-soluble resin C solution was obtained in the same manner as in Synthesis Example 4, except that 40 parts by mass of styrene was used instead of BzMA. The solid content was 40% by mass, the acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

(Synthesis Example 7: Synthesis of Coloring Material A)
5.0 g of Acid Red 289 was added to 500 ml of water and dissolved at 80 ° C. to prepare a dye solution. 3.85 g of polyaluminum chloride ("Takibain # 1500" manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5% by mass, alumina content 23.5% by mass) in 200 ml of water Then, the mixture was stirred and 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 the mixture was further stirred at 80 ° C. for 1 hour. The formed precipitate was collected by filtration and washed with water. The cake thus obtained was dried to obtain 6.30 g (yield 96.2%) of the metal lake coloring material A of the rhodamine-based acid dye.

(Colored Resin Composition Production Example 1)
(1) Production of color material dispersion liquid 1
13.3 parts by mass of the block copolymer A of Synthesis Example 3 was used as the dispersant, and C.I. I. Pigment Green 59 (PG59, trade name FASTOGEN GREEN C100, manufactured by DIC Corporation), 13.0 parts by mass, 10.0 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 4, and 63.7 parts by mass of PGMEA. Part, 100 parts by mass of zirconia beads having a particle size of 2.0 mm are put in a mayonnaise bottle, and shaken for 1 hour by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing, and then zirconia beads having a particle size of 2.0 mm are taken out. Then, 200 parts by mass of zirconia beads having a particle diameter of 0.1 mm was added, and similarly disintegrated and dispersed for 4 hours with a paint shaker to obtain a color material dispersion liquid 1.

(2) Production of Photosensitive Colored Resin Composition 1 for Color Filter 66.4 parts by mass of the color material dispersion liquid 1 obtained in the above (1), and 5. the alkali-soluble resin A solution obtained in Synthesis Example 4 were used. 94 parts by mass, 4.64 parts by mass of a photopolymerizable compound (trade name Aronix M-520D, manufactured by Toagosei Co., Ltd.), 1.18 parts by mass of the compound A1 obtained in Synthesis Example 1 as a photoinitiator. And PGMEA were added in an amount of 19.58 parts by mass to obtain a photosensitive colored resin composition 1 for a color filter.

(Colored resin composition production examples 2 to 11, Colored resin composition production examples 101 to 106)
In the colored resin composition production example 1, instead of using 1.18 parts by mass of the compound A1 obtained in Synthesis Example 1 as the photoinitiator, the photoinitiators shown in Tables 1 and 2 are shown in Tables 1 and 2. Photosensitive colored resin compositions 2 to 11 and 101 to 106 for color filters were obtained in the same manner as in Colored Resin Composition Production Example 1 except that the used amount was changed.

(Colored Resin Composition Production Example 12)
In Production Example 3 of the colored resin composition, C.I. I. Pigment Green 59 (PG59) instead of C.I. I. A photosensitive colored resin composition 12 for a color filter was obtained in the same manner as in Colored Resin Composition Production Example 3 except that Pigment Red 254 (PR254) was used.

(Colored Resin Composition Production Example 13)
In the production example 1 of the colored resin composition, C.I. I. Pigment Green 59 (PG59) was used instead of Acid Red 289 (AR289) (xanthene dye) in the same manner as in Colored Resin Composition Production Example 1 to prepare a photosensitive colored resin composition 13 for a color filter. Obtained.

(Colored Resin Composition Production Example 107)
In Colored Resin Composition Production Example 101, C.I. I. Pigment Green 59 (PG59) was used instead of Acid Red 289 (AR289) (xanthene dye) in the same manner as in Colored Resin Composition Production Example 101 to prepare a photosensitive colored resin composition 107 for a color filter. Obtained.

(Colored Resin Composition Production Example 14)
In the production example 1 of the colored resin composition, C.I. I. Pigment Green 59 (PG59) was used in place of the coloring material A obtained in Synthesis Example 7 in the same manner as in Colored Resin Composition Production Example 1 to prepare a photosensitive colored resin composition 14 for a color filter. Obtained.

(Colored Resin Composition Production Example 15)
In the production example 7 of the colored resin composition, C.I. I. Pigment Green 59 (PG59) was used in place of the color material A obtained in Synthesis Example 7, and the alkali-soluble resin A solution was used in place of the alkali-soluble resin A solution. In the same manner as above, a photosensitive colored resin composition 15 for color filter was obtained.

(Colored Resin Composition Production Example 16)
In the production example 7 of the colored resin composition, C.I. I. Pigment Green 59 (PG59) was used in place of the color material A obtained in Synthesis Example 7, and the alkali-soluble resin A solution was used in place of the alkali-soluble resin A solution. In the same manner as described above, a photosensitive colored resin composition 16 for color filter was obtained.

[Evaluation]
(1) Residual film rate The photosensitive colored resin composition obtained in each of the colored resin composition production examples was applied onto a glass substrate (NH Techno Glass Co., Ltd., "NA35") using a spin coater. After that, it was dried at 80 ° C. for 3 minutes using a hot plate to form a coating film on the glass substrate. Ultraviolet light of 60 mJ / cm ² was applied to the entire surface using an ultrahigh pressure mercury lamp without using a photomask, and a coating film was formed after exposure. Then, a 0.05 wt% potassium hydroxide aqueous solution was spin-developed as a developing solution, and the developing solution was subjected to an indirect solution for 60 seconds and then washed with pure water to perform a development treatment to form a coating film after development. Then, post-baking was performed in a clean oven at 230 ° C. for 25 minutes to form a cured coating film (colored layer) having a thickness of 3.0 μm. In the process of forming a coating film, the film thickness after exposure (E), the film thickness after development (D), and the film thickness after post-baking (B) were measured by a stylus profiler P-16 (manufactured by KLA-Tencor). And the film thickness (D) / (E) after development was calculated.
In addition, when the film thickness (D) / (E) after development is 95% or more, it is in a range suitable for actual use.

(2) Line width increase / decrease rate The photosensitive colored resin composition obtained in each colored resin composition production example was placed on a glass substrate ("NH35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater. After coating so that the cured coating film had a thickness of 3.0 μm, it was dried at 80 ° C. for 3 minutes using a hot plate to form a coating film on a glass substrate. This coating film is exposed to ultraviolet rays of 60 mJ / cm ² using an ultrahigh pressure mercury lamp through an independent fine line pattern photomask having a line width of 1 μm to 100 μm to form a post-exposure coating film on a glass substrate, Next, a 0.05 mass% potassium hydroxide aqueous solution is used as a developing solution for spin development, and the developing solution is subjected to an indirect solution for 60 seconds and then washed with pure water for development processing, and then in a clean oven at 230 ° C. for 25 minutes. It was post-baked to form a fine line pattern. Of the formed fine line pattern, the width of the fine line pattern at the portion where the opening width of the chrome mask during exposure was 90 μm was measured with an optical microscope, and the line width increase / decrease rate was calculated from the fine line pattern width / mask opening width.

<Evaluation criteria>
A: Within ± 0.3% of the target line width B: Over ± 0.3% of the target line width Within ± 0.5% C: ± 0 of the target line width Exceeding 5% ± 1.0% or less

(3) Electrical Reliability A pair of ITO substrates A and B having ITO (indium tin oxide) electrodes provided on the surface of a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) are prepared, and one ITO substrate is prepared. The photosensitive colored resin composition obtained in each of the colored resin composition production examples was applied onto the surface of the ITO substrate of A by a spin coater and dried on a hot plate at 80 ° C. for 3 minutes to form a coating film. Next, the coating film was irradiated with an ultraviolet ray of 60 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. After irradiation, the substrate was developed with a 0.05 wt% potassium hydroxide aqueous solution for 1 minute by a spin developing machine, washed with pure water for 1 minute, and dried. After drying, the substrate was post-baked in an oven at 230 ° C. for 25 minutes to prepare a colored layer arranged in a pattern on the substrate.

(Production of liquid crystal cell)
Further, the ITO substrate B is prepared, and an epoxy resin-based sealant containing silica beads having a diameter of 5 μm is applied on the outer periphery of the substrate, and then the ITO having the colored layer arranged in the pattern is formed. The colored layer surfaces of the substrate A were arranged facing each other and heated in an oven at 180 ° C. for 2 hours. Liquid crystal (MLC-6846-000, manufactured by Merck Japan Co., Ltd.) was injected into the empty cells formed between the pressure-bonded substrates, and the periphery was sealed with a UV-curable sealant to measure the voltage holding ratio. A liquid crystal cell was produced. The liquid crystal has a voltage holding ratio of 98% or more under the following voltage holding ratio measuring conditions.

(Voltage holding ratio)
Using the liquid crystal cell obtained above, the ITO substrates A and B were separated under the conditions of ITO electrode distance: 5 μm, applied voltage pulse amplitude: 5 V, applied voltage pulse frequency: 60 Hz, applied voltage pulse width: 16.67 msec. The voltage holding ratio was measured by applying a pulse voltage to the sample and using a voltage holding ratio measuring system (VHR-1A manufactured by Toyo Technica Co., Ltd.).

<Evaluation criteria>
A: Voltage holding ratio is 90% or more (display stability of liquid crystal is more excellent)
B: Voltage holding ratio is 80% or more and less than 90% (excellent liquid crystal display stability)
C: Voltage holding ratio is less than 80% (the alignment state of the liquid crystal is abnormally changed to cause display failure of the liquid crystal)
A, B and above are within the practical range.

(4) Optical performance evaluation, contrast evaluation The photosensitive colored resin composition obtained in each colored resin composition production example was placed on a glass substrate (NH Techno Glass Co., Ltd., "NA35") with a spin coater. After coating using a hot plate, it was dried at 80 ° C. for 3 minutes using a hot plate to form a coating film on a glass substrate. Ultraviolet light of 60 mJ / cm ² was applied to the entire surface using an ultrahigh pressure mercury lamp without using a photomask, and a coating film was formed after exposure. Then, a 0.05 wt% potassium hydroxide aqueous solution was spin-developed as a developing solution, and the developing solution was subjected to an indirect solution for 60 seconds and then washed with pure water to perform a development treatment to form a coating film after development. After that, post-bake in a clean oven at 230 ° C. for 25 minutes, y = 0.40 when G59 is used, x = 0.65 when R254 is used, and when AR289 and color material A are used. , Y = 0.048, a cured coating film (colored layer) was formed.
The contrast, chromaticity (x, y), and brightness (Y) of each colored layer were measured using a contrast measuring device CT-1B manufactured by Tsubosaka Electric and a microspectroscopic measuring device OSP-SP200 manufactured by Olympus.

Abbreviations in Tables 1 and 2 are as follows.
NCI-930: oxime ester photoinitiator (trade name NCI-930, manufactured by ADEKA)
OXE-02: oxime ester-based photoinitiator (trade name Irgacure OXE-02, manufactured by BASF)
OXE-01: oxime ester-based photoinitiator (trade name Irgacure OXE-01, manufactured by BASF)
-Irg369: α-aminoketone photoinitiator (Irgacure 369, manufactured by BASF)
Irg907: α-aminoketone photoinitiator (Irgacure 907, manufactured by BASF)
-Mercapto-based: Mercapto-based chain transfer agent (2-mercaptobenzothiazole, manufactured by Tokyo Kasei)
・ Biimidazole-based: Biimidazole-based photoinitiator (HABI, manufactured by Kurogane Kasei)
-DETX: thioxanthone photoinitiator (DOUBLECURE DETX, Double Bond Chemical)
-Irg819: Acylphosphine oxide photoinitiator (Irgacure 819, manufactured by BASF

  Moreover, in Tables 1-2, a compounding composition (mass part) is a mass ratio of the solid content in a colored resin composition.

<Summary of results>
The photosensitive colored resin compositions of Colored Resin Composition Production Examples 1 to 16 containing the compound represented by the general formula (A) as a photoinitiator have excellent curability even when the coloring material concentration is high. However, it was revealed that the photosensitive colored resin composition had a high residual film rate. Further, the photosensitive colored resin compositions of Colored Resin Composition Production Examples 1 to 16 containing the compound represented by the general formula (A) as a photoinitiator are excellent in the evaluation of the voltage holding ratio, and thus the color filter. The effect of improving the reliability of was also clarified. When a dye is used as a coloring material, there is a concern that the reliability may decrease due to easy exudation, but according to the present invention, the exudation of the dye is suppressed as compared with the conventional case, and the reliability of the color filter is improved. It was clarified (comparison between colored resin composition production example 13 and colored resin composition production example 107).
Further, as a photoinitiator, an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator is added to the compound represented by the general formula (A). Further, it has been clarified that the ability to form a fine line pattern according to the design of the mask line width is improved when the fine line pattern is formed by further using at least one of the above and a mercapto chain transfer agent (coloring resin. Comparison between Composition Production Example 1 and Colored Resin Composition Production Examples 2 to 11).
On the other hand, in the colored resin composition production example 101 using the oxime ester-based photoinitiator that does not satisfy the general formula (A) as the photoinitiator, the residual film rate was low and the voltage retention rate was also poor. In Colored Resin Composition Production Example 102 and Colored Resin Composition Production Example 103 using the α-aminoketone photoinitiator as the photoinitiator, the residual film rate was low and the voltage retention rate was also inferior. As the photoinitiator, a colored resin composition Production Example 104 in which a monooxime ester photoinitiator that does not satisfy the general formula (A) is combined with an α-aminoketone photoinitiator also has a low residual film ratio and a voltage holding ratio. It was inferior.

  Since the photosensitive colored resin composition containing the specific photoinitiator of the present invention has excellent curability and a high residual film rate, it is widely used for manufacturing various displays and the like.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Coloring 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 Reference Signs List 76 cathode 80 organic light emitter 100 organic light emitting display device

Claims (5)

Contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The photoinitiator contains a compound represented by the following general formula (A),
The photoinitiator is further contain α- aminoketone photoinitiators,
The content of the compound represented by the general formula (A) is 5 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the total amount of the photoinitiator, and the photosensitive colored resin composition for a color filter. object.

[In general formula (A), R < ¹¹ > is a C1-C5 alkyl group or a C1-C5 alkoxy group. R ¹² is a group having 1 to ¹² carbon atoms. R ¹³ is a group represented by the general formula (B) or the general formula (C). Y is a sulfur atom or an oxygen atom. ]

[In General Formula (B) and General Formula (C), Z is an oxygen atom, a sulfur atom, or -N (R _z )-(R _z is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); Each hydrogen atom in (B) and general formula (C) may be substituted. ] The color according to claim 1, further comprising a dispersant, and the dispersant includes a polymer having a structure represented by the following general formula (I) and having an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less. Photosensitive colored resin composition for filters.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms, and- [CH (R ⁵ ). _{^{-CH (R 6) -O] x}} -CH (R 5) -CH (R 6) - or _{- [(CH 2) y -O} ] z - (CH 2) y - 2 monovalent organic group represented by , R ³ and R ⁴ each independently represent a optionally substituted linear or cyclic hydrocarbon group, R ³ and R ⁴ form a ring structure by bonding with each other .R ⁵ and R Each of ⁶ is independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )   The colored resin composition for a color filter according to claim 1 or 2, wherein the alkali-soluble resin is a resin having a hydrocarbon ring.   A color filter comprising at least a transparent substrate and a coloring layer provided on the transparent substrate, wherein at least one of the coloring layers is a photosensitive coloring for a color filter according to any one of claims 1 to 3. A color filter having a colored layer made of a cured product of a resin composition.   A display device comprising the color filter according to claim 4.

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