JP2017167399A - Photosensitive coloring resin composition for color filter, color filter, and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring resin composition that has excellent hardenability, has a high residual film ratio, and reduces a variation in sensitivity even after cold storage.SOLUTION: There is provided a photosensitive coloring resin composition for a color filter that contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, where the photoinitiator contains a compound represented by the following general formula (1). Codes in the general formula (1) are as defined in the specification.SELECTED DRAWING: None

Description

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

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (cell phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. As a light source at that time, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. In the organic light emitting display device, a color filter is used for color adjustment.
Under such circumstances, demands for higher luminance, higher contrast, and improved color reproducibility are increasing in color filters.

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

  As for color filters, there is a growing demand for higher brightness, higher contrast, and improved color reproducibility, and as a result, the color material concentration in the colored layer of the color filter is higher than before, so that photopolymerization is relatively possible. The components required for the patterning have decreased and patterning has become difficult. Furthermore, in order to improve the productivity of the color filter, the integrated exposure amount necessary for patterning is reduced, and how to ensure the curability necessary for patterning is a big 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).
Patent Document 2 proposes to use an oxime ester compound having two oxime ester groups in the molecule as a photopolymerization initiator as a photosensitive resin composition capable of achieving high sensitivity.

Japanese Patent No. 3993725 Chinese Patent Application No. 10614940

Conventionally, even when using an oxime ester compound that has been considered to be able to achieve high sensitivity, for example, when the colorant concentration is high or the integrated exposure amount is small, the curability is insufficient and the remaining film ratio is low. There was a problem that there was a tendency to become insufficient.
Furthermore, the photosensitive colored resin composition may be used after refrigerated storage. However, when an oxime ester compound that has been said to be able to achieve high sensitivity is used, variations in sensitivity occur during exposure, resulting in low productivity. There was a case.

  The present invention has been made in view of the above circumstances, has a high curability, has a high residual film ratio, and is less susceptible to variations in sensitivity even after refrigerated storage. It is an object of the present invention to provide a color filter formed using a photosensitive colored resin composition for a filter and a display device having excellent display characteristics by using the color filter.

The photosensitive colored resin composition for a color filter according to the present invention 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 (1).

(In General Formula (1), W ¹ and W ² each independently represent a carbonyl bond (—CO—) or a single bond, and at least one of W ¹ and W ² is a carbonyl bond (—CO—). R ^a is an alkyl group having 2 to 6 carbon atoms, R ^b is an alkyl group having 4 to 10 carbon atoms, R ^c includes at least a hydrocarbon ring or a heterocyclic ring, and further has 1 to 4 carbon atoms. An alkylene chain, a thioether bond (—S—), an ether bond (—O—), and a carbonyl bond (—CO—), which may contain at least one divalent linking group. R ^b and R ^c are different from each other, and R ^d and R ^e are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

The color filter according to 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 the color filter photosensitivity according to the present invention. It has the colored layer which consists of hardened | cured material of a colored resin composition, It is characterized by the above-mentioned.
The present invention also provides a display device having the color filter according to the present invention.

  According to the present invention, there is provided a photosensitive colored resin composition having excellent curability, a high residual film ratio, and less susceptible to variations in sensitivity even after refrigerated storage, and the photosensitive colored resin composition for color filters. By using the color filter formed by using the color filter, a display device having excellent display characteristics can be provided.

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

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 invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.

I. Photosensitive colored resin composition The photosensitive colored resin composition for a color filter according to the present invention 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 (1).

(In General Formula (1), W ¹ and W ² each independently represent a carbonyl bond (—CO—) or a single bond, and at least one of W ¹ and W ² is a carbonyl bond (—CO—). R ^a is an alkyl group having 2 to 6 carbon atoms, R ^b is an alkyl group having 4 to 10 carbon atoms, R ^c includes at least a hydrocarbon ring or a heterocyclic ring, and further has 1 to 4 carbon atoms. An alkylene chain, a thioether bond (—S—), an ether bond (—O—), and a carbonyl bond (—CO—), which may contain at least one divalent linking group. R ^b and R ^c are different from each other, and R ^d and R ^e are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

  The photosensitive colored resin composition for a color filter according to the present invention has excellent curability and a high residual film ratio by using the compound represented by the general formula (1) as a photoinitiator, In addition, it is possible to produce a photosensitive colored resin composition that is less susceptible to variations in sensitivity even after refrigerated storage. In particular, for example, when the color material concentration is high or the integrated exposure amount is small, it has been difficult to produce a colored resin composition with excellent curability and a high residual film ratio in the prior art. Even in such a case, the photosensitive colored resin composition for a color filter according to the present invention has excellent curability, a high residual film ratio, and sensitivity does not easily vary even after refrigerated storage. A photosensitive colored resin composition can be produced.

By using the compound represented by the general formula (1) as a photoinitiator, the effect of exerting the above-described effects is unclear but is estimated as follows.
First, since the compound represented by the general formula (1) used in the present invention has two oxime ester groups with respect to one carbazole ring which is a light absorbing part, Can generate radicals efficiently. Therefore, for example, even if the color material concentration in the colored resin composition is increased or the integrated exposure amount is small, it is estimated that excellent curability is obtained and the remaining film ratio is improved.
In addition, when a compound having two oxime ester groups with respect to one carbazole ring, which has been disclosed in the past, is used as a photoinitiator, variations in sensitivity occur after refrigerated storage, as shown in a comparative example described later. There was a problem to do. It is estimated that the sensitivity variation is caused by partial precipitation of a photoinitiator having low solvent solubility after refrigerated storage or when used at a high concentration.
On the other hand, the compound represented by the general formula (1) used in the present invention tends to have a structure with high crystallinity because the carbazole ring is rigid, so that the carbazole ring is linked to two oxime ester groups. R ^b and R ^c are substituents different from each other in the chemical structure of the two oxime ester groups, and R ^b is an alkyl group having 4 to 10 carbon atoms. , R ^c is a specific substituent containing at least a hydrocarbon ring or a heterocyclic ring, whereby a compound having an asymmetric structure is obtained, so that the crystallinity is lowered. Therefore, the compound represented by the general formula (1) used in the present invention has high solvent solubility and compatibility. For example, it is precipitated during exposure even after refrigerated storage or when used at a high concentration. It is estimated that the sensitivity is less likely to vary.
Furthermore, according to the photosensitive colored resin composition of the present invention, since excellent curability is obtained, components such as color materials in the cured product are confined, so that the color filter is manufactured and the display device is driven. Occasionally, these components were prevented from seeping out, and the effect of improving the reliability of the color filter was also found.

The photosensitive colored resin composition for a color filter according to the present invention of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. Other components may be contained as long as the effects are not impaired.
Hereinafter, each component of the photosensitive colored resin composition of the present invention will be described in detail in order from the photoinitiator characteristic of the present invention.

[Photoinitiator]
<Compound represented by the general formula (1)>
The photoinitiator used in the present invention contains a compound represented by the following general formula (1).

(In General Formula (1), W ¹ and W ² each independently represent a carbonyl bond (—CO—) or a single bond, and at least one of W ¹ and W ² is a carbonyl bond (—CO—). R ^a is an alkyl group having 2 to 6 carbon atoms, R ^b is an alkyl group having 4 to 10 carbon atoms, R ^c includes at least a hydrocarbon ring or a heterocyclic ring, and further has 1 to 4 carbon atoms. An alkylene chain, a thioether bond (—S—), an ether bond (—O—), and a carbonyl bond (—CO—), which may contain at least one divalent linking group. R ^b and R ^c are different from each other, and R ^d and R ^e are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

In the general formula (1), W ¹ and W ² are each independently a carbonyl bond (—CO—) or a single bond, but at least one of W ¹ and W ² is a carbonyl bond (—CO—) Therefore, it is estimated that the solvent solubility and compatibility are improved.
In general formula (1), it is preferable that W ¹ and W ² are both carbonyl bonds (—CO—) from the viewpoint of improving solvent solubility and compatibility and making it difficult for variations in sensitivity to occur even after refrigerated storage. .

R ^a is an alkyl group having 2 to 6 carbon atoms, and the alkyl group may be a linear, branched, cyclic, or a combination thereof. For example, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, cyclopentyl group, methylcyclopentyl group, cyclopentylmethyl group, A cyclohexyl group etc. are mentioned. R ^a is preferably an alkyl group having 2 to 6 carbon atoms, more preferably an ethyl group or a linear or branched propyl group.

R ^b is an alkyl group having 4 to 10 carbon atoms, and the alkyl group may be any of linear, branched, cyclic, or a combination thereof. For example, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, methylcyclopentyl group, cyclopentylmethyl group, cyclohexyl group, n-heptyl group, cyclopentylethyl group Cyclohexylmethyl group, cycloheptyl group, n-octyl group, n-nonyl group, 2-ethyl-n-octyl group, n-decyl group and the like. Among these, ^Rb is preferably a linear alkyl group having 4 to 10 carbon atoms from the viewpoint of improving solvent solubility and compatibility and making it difficult for variations in sensitivity to occur even after refrigerated storage.

R ^c contains at least a hydrocarbon ring or a heterocyclic ring, and further selected from an alkylene chain having 1 to 4 carbon atoms, a thioether bond (—S—), an ether bond (—O—), and a carbonyl bond (—CO—). It is a group which may contain at least one kind of divalent linking group. The hydrocarbon ring may be either an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. Examples of the aliphatic hydrocarbon ring include cyclopentane, cyclohexane, and cycloheptane. Examples of the aromatic hydrocarbon ring include benzene and naphthalene. The heterocyclic ring is preferably a heterocyclic ring containing at least one of a nitrogen atom and an oxygen atom, and may be either an aliphatic heterocyclic ring or an aromatic heterocyclic ring. Examples of the aliphatic heterocycle include tetrahydrofuran, pyrrolidine, dioxolane, tetrahydropyran, piperidine, morpholine and the like, and examples of the aromatic heterocycle include pyrrole, furan, oxazole, imidazole, pyridine, pyrimidine and the like. These hydrocarbon rings or heterocyclic rings may further have a substituent such as an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group. These hydrocarbon rings or heterocyclic rings are preferably 5-membered or 6-membered rings from the viewpoint of improving solvent solubility and compatibility, and making it difficult for variations in sensitivity to occur after refrigerated storage. , Cyclopentane, cyclohexane, dioxolane, pyrimidine and the like are preferably used.
In R ^c , the hydrocarbon ring or heterocyclic ring may be directly bonded to the carbon atom of the oxime ester group, and among them, an alkylene chain having 1 to 4 carbon atoms, a thioether bond (—S—), an ether bond Solvent solubility and compatibility with the carbon atom of the oxime ester group through at least one divalent linking group selected from (—O—) and carbonyl bond (—CO—). It is preferable from the viewpoint that the sensitivity is less likely to vary even after refrigerated storage. In such a divalent linking group, the alkylene chain having 1 to 4 carbon atoms may be any of linear or branched alkylene chains having 1 to 4 carbon atoms, such as methylene, ethylene, propylene, Butylene is mentioned. The linking group may be a thioether bond (—S—), an ether bond (—O—), or a carbonyl bond (—CO—), a thioether bond (—S—), an ether bond (—O—). And a group comprising a combination of at least one selected from a carbonyl bond (—CO—) and an alkylene chain having 1 to 4 carbon atoms. Among them, the number of carbon atoms, oxygen atoms, and sulfur atoms constituting the divalent linking group is preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less. As the divalent linking group, among them, methylene, ethylene, thioether bond (-S-), or ether bond (from the viewpoint of improving the solvent solubility and compatibility and making it difficult to vary the sensitivity even after refrigerated storage. -O-) is preferred.

R ^d and R ^e are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group, and examples of the alkyl group having 1 to 6 carbon atoms include a methyl group and an alkyl group having 2 to 6 carbon atoms. As for, the same as described for ^Ra can be used.
Among them, R ^d and R ^e are preferably an ethyl group or a methyl group, and more preferably a methyl group from the viewpoint of sensitivity.

From the viewpoint of reducing the content of the photoinitiator, the molecular weight of the compound represented by the following general formula (1) is:
It is preferably 1,000 or less, and more preferably 800 or less.

As the compound represented by the general formula (1), for example, R ^a is an ethyl group, W ¹ and W ² are both carbonyl bonds (—CO—), and R ^b has 4 to 10 carbon atoms. A compound in which R is ^a straight-chain alkyl group, R ^c is a cyclohexylmethyl group, R ^d and R ^e are methyl groups; R ^a is an ethyl group, and W ¹ and W ² are both carbonyl bonds (—CO—) R ^b is a linear alkyl group having 4 to 10 carbon atoms, R ^c is a cyclopentylethyl group, R ^d and R ^e are methyl groups; R ^a is an ethyl group, and W ¹ And W ² are both carbonyl bonds (—CO—), R ^b is a linear alkyl group having 4 to 10 carbon atoms, R ^c is a pyrimidylthio group optionally substituted with a methyl group, compound ^d and ^{R e} is a methyl group; ^{R a} is An ethyl group, W ¹ and W ² are both carbonyl bonds (—CO—), R ^b is a linear alkyl group having 4 to 10 carbon atoms, and R ^c is substituted with a methyl group. A compound which is a good pyrimidyloxy group, R ^d and R ^e are methyl groups; R ^a is an ethyl group, W ¹ and W ² are both carbonyl bonds (—CO—), and R ^b has 4 to 4 carbon atoms Preferred examples include compounds having 10 linear alkyl groups, R ^c is a dioxolane methyl group which may be substituted with a methyl group, and R ^d and R ^e are methyl groups. It is not limited to.

  As a compound represented by the said General formula (1), the at least 1 compound chosen from the following compounds 1-16 is mentioned as a more suitable thing.

  The compound represented by the general formula (1) can be synthesized with reference to, for example, Japanese Patent No. 4600600.

  The compound represented by the general formula (1) 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, but the general formula (1) You may use in combination with the other photoinitiator different from the compound represented by these. The photoinitiator used for the photosensitive colored resin composition of the present invention includes a chain transfer agent in addition to the photopolymerization initiator.

<Other photoinitiators>
Other photoinitiators include, for example, dioxime ester initiators containing two oxime ester groups in the molecule different from the compound represented by the general formula (1), and oximes containing one oxime ester group in the molecule. Examples include ester initiators, α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acyl phosphine oxide photoinitiators, and mercapto chain transfer agents.
Among them, when forming a fine line pattern, the compound represented by the general formula (1) from the viewpoint that the linearity is further improved or the ability to form a fine line pattern as designed for the mask line width is improved, It is preferable to use a combination of at least one of an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent.
“Improved linearity” means that the end of the colored layer formed in the development step after applying the colored composition has few irregularities and is linear or substantially linear.

Since the α-aminoketone photoinitiator has the property of curing the middle from the surface of the coating film and easily suppresses the coating film deep curability, the coating film is combined with the compound represented by the general formula (1). It is preferable from the viewpoint of a high tendency to improve deep part curability.
Examples of the α-aminoketone photoinitiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (Dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg 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.
The α-aminoketone photoinitiator may be used alone or in combination of two or more thereof. Among them, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and When 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone is used in combination, it is preferable from the viewpoint of improving the remaining film ratio.

The biimidazole photoinitiator has the property of curing the deep part of the coating film, easily suppresses the coating film surface curability, and when combined with the compound represented by the general formula (1), It is preferable from the viewpoint of a high tendency to improve.
Examples of the biimidazole 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.
As a biimidazole photoinitiator, you may use individually or in combination of 2 or more types, and it is preferable to use a mercapto chain transfer agent especially from the point which improves coating-film hardenability.
Moreover, when the compound represented by the general formula (1) is further used in combination with a biimidazole photoinitiator and the α-aminoketone photoinitiator, the remaining film rate and pattern linearity are improved. preferable.

Examples of the thioxanthone photoinitiator include 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-dichlorothioxanthone, and the like.
The thioxanthone photoinitiator may be used alone or in combination of two or more. Among them, the use of 2,4-isopropylthioxanthone and 2,4-diethylthioxanthone improves the radical generation transfer. preferable.
In addition, it is preferable to use a combination of the thioxanthone photoinitiator and the α-aminoketone photoinitiator in combination with the compound represented by the general formula (1) from the viewpoint of improving the remaining film rate.

Although acylphosphine oxide photoinitiators have the property of being less susceptible to yellowing due to heat, they are generally low in sensitivity and may not provide sufficient curability, but are represented by the general formula (1). In combination with a compound having a high tendency to improve the overall film curability.
Examples of the acylphosphine oxide photoinitiator include benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 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 photoinitiator may be used alone or in combination of two or more. Among them, it is preferable to use bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide for coating film curability. Is preferable from the viewpoint of improvement.

A mercapto chain transfer agent has a property of receiving a radical from a slowly reacting radical and accelerates the reaction, and is particularly preferable when combined with a biimidazole photoinitiator because 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, 3- 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-mercaptobuty Rate), pen Erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) and the like.
The mercapto chain transfer agent may be used alone or in combination of two or more. Among them, it is preferable to use 2-mercaptobenzothiazole from the viewpoint of improving the reaction rate.

The total content of the photoinitiator used in the photosensitive colored resin composition for a color filter 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 photosensitive colored resin composition for a color filter is not limited. Preferably it is 0.1 mass% or more and 12.0 mass% or less with respect to the total amount, More preferably, it exists in the range of 1.0 mass% or more and 8.0 mass% or less. When this content is not less than the above lower limit, photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development. On the other hand, if it is not more than the above upper limit, the yellowing of the resulting colored layer becomes strong and the luminance Can be suppressed.
In addition, solid content is all except a solvent, and a liquid polyfunctional monomer etc. are also contained.

  The content of the compound represented by the general formula (1) used in the photosensitive colored resin composition for color filters of the present invention is preferably based on the total solid content of the photosensitive colored resin composition for color filters. 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 this content is not less than the above lower limit, photocuring is sufficiently advanced and the exposed portion is prevented from being eluted during development. On the other hand, if the content is not more than the above upper limit, the yellowing of the resulting colored layer becomes strong and the luminance is reduced. Can be suppressed.

When using together the compound represented by the said General formula (1) and the said other photoinitiator as a photoinitiator used for this invention, content of the compound represented by the said General formula (1) 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 a total of 100 parts by mass of the photoinitiator used in the photosensitive colored resin composition of the present invention. It is still more preferable, and it is still more preferable that it is 30 mass parts or more.
On the other hand, the content of the compound represented by the general formula (1) is 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 photoinitiators. It is preferable that it is 95 mass parts or less in a total of 100 mass parts of initiator, and it is more preferable that it is 85 mass parts or less.

  The photoinitiator used in the present invention is 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 selected from the above, the total content thereof is 0.2% by mass or more and 4.0% by mass or less, and further 0.5% with respect to the total solid content of the photosensitive colored resin composition for color filters. It is preferable that it is in the range of not less than 2.0% by mass and not more than 2.0% by mass in order to sufficiently exhibit the combined effect with these photoinitiators.

  As a photoinitiator used in the present invention, a compound represented by the general formula (1) is combined with an α-aminoketone photoinitiator and a biimidazole photoinitiator and / or a thioxanthone photoinitiator. The ratio of the α-aminoketone photoinitiator and the biimidazole photoinitiator and / or the thioxanthone photoinitiator is 100 parts by mass of the α-aminoketone photoinitiator and the biimidazole photoinitiator and The thioxanthone 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.

[Color material]
In the present invention, the color material is not particularly limited as long as it can form a desired color when a colored layer of a color filter is formed. Various organic pigments, inorganic pigments, dispersible dyes, and dyes are not particularly limited. Can be used alone or in admixture of two or more. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.

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 and 7.

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

  For example, when forming the pattern of the light shielding layer on the substrate of the 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 blended in the ink. As the black pigment having a high light shielding property, for example, an inorganic pigment such as carbon black or iron trioxide or an organic pigment such as cyanine black can be used.

Examples of the dispersible dye include dyes (lake pigments) that have become dispersible by adding various substituents to the dye, or insolubilizing in a solvent using a known rake (chlorination) technique. And dyes that are dispersible by using in combination with a low solvent. By using such a dispersible dye in combination with the dispersant, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. Xanthene dyes are preferred because of their high heat resistance. The xanthene acid dye preferably has a compound represented by the following general formula (III), that is, a rhodamine acid dye.

(In General Formula (III), R ^{I to} R ^IV each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R ^I and R ^III , R ^II and R ^IV are bonded to each other. A ring structure may be formed, R ^V represents an acidic group, X represents a halogen atom, m represents an integer of 0 to 5. General Formula (III) has one or more acidic groups. , 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. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. More preferably, it is a linear or branched alkyl group having 1 to 5 carbon atoms. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and the like, and the substituted alkyl group includes a benzyl group, and further, a substituent. May have a halogen atom or an acidic group.
The aryl group in R ^{I to} R ^IV is not particularly limited. For example, the aryl group which may have a C6-C20 substituent is mentioned, Especially, group which has a phenyl group, a naphthyl group, etc. is preferable. Examples of the heteroaryl group in R ^{I to} R ^IV include a heteroaryl group that may have a substituent having 5 to 20 carbon atoms, and those containing a nitrogen atom, an oxygen atom, or a sulfur atom as the hetero atom are preferable. .
Examples of the substituent that the aryl group or heteroaryl group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, a carbamoyl group, and a carboxylic acid ester group. .
R ^{I to} R ^IV may be the same or different.

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

As the compound represented by the general formula (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 increasing brightness.
From the viewpoint of heat resistance, a compound having a betaine structure in which m = 1 and n = 0 in general formula (III) is preferable.
Moreover, 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 from the viewpoint that a colored layer excellent in luminance and light resistance can be formed.
Although the manufacturing method of the compound represented by the said general formula (III) is not specifically limited, For example, it can obtain by referring to Unexamined-Japanese-Patent No. 2010-211198.

In the metal lake color material of the xanthene acid dye, those containing a metal atom are used as a lake agent. By using a rake agent containing a metal atom, the heat resistance of the coloring material is increased. As such a rake agent, a rake agent containing a metal atom that becomes a divalent or higher valent metal cation is preferable.
As a guide, if the amount of dye dissolved in 10 g of 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 size of the color material used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a color layer of a color filter, and varies depending on the type of color material used. Is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle diameter of the color material is in the above range, the display device including the color filter manufactured using the color material dispersion according to the present invention has high contrast and high quality. it can.
The average primary particle diameter of the color material in the present invention represents “volume distribution median diameter (D50)”. The average primary particle size of the coloring material is obtained by scanning transmission electron by attaching a dedicated bright field STEM sample stage 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”), take a STEM photo of 200,000 times, import it into the following software, select 100 color materials on the photo, and select each diameter (pass length) And 50% cumulative particle size by volume from the volume-based distribution.

  The coloring material used in the present invention can be produced 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 refined.

  The total content of the coloring material may be blended in a proportion of 3% by mass to 65% by mass, more preferably 4% by mass to 60% by mass with respect to the total solid content of the photosensitive colored resin composition for color filters. preferable. If it is more than the said lower limit, the colored layer at the time of apply | coating the photosensitive colored resin composition for color filters to predetermined | prescribed film thickness (usually 1.0 micrometer-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. In particular, when a colored layer having a high color material concentration is formed, the total content of the color material is preferably 15% by mass to 65% by mass, more preferably 15% by mass to 65% by mass with respect to the total solid content of the photosensitive color resin composition for color filters. Is preferably blended at a ratio of 25 mass% to 60 mass%.

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

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

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring that is a bulky group in the alkali-soluble resin, shrinkage during curing is suppressed, peeling from the substrate is eased, and substrate adhesion is improved. Further, the present inventors have found that the use of an alkali-soluble resin having a hydrocarbon ring suppresses the solvent resistance of the obtained colored layer, particularly the swelling of the colored layer. Although the action is unclear, the bulky hydrocarbon ring in the colored layer suppresses the movement of molecules in the colored layer, resulting in an increase in the strength of the coating and suppression of swelling by the solvent. It is estimated that.
Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and combinations thereof. May have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group or an amide group. Especially, when an aliphatic ring is included, while the heat resistance and adhesiveness of a colored layer improve, the brightness | luminance of the obtained colored layer improves.
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 (IV) It is done.

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

In the alkali-soluble resin used in the present invention, it is easy to adjust the amount of each constituent unit by using an acrylic copolymer having a constituent unit having a hydrocarbon ring separately from the constituent unit having a carboxyl group. This is preferable because the amount of the structural unit having a hydrocarbon ring is increased to easily improve the function of the structural unit.
An acrylic copolymer having a carboxyl-containing structural unit and the hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the aforementioned “other copolymerizable monomer”. Can do.
Examples of the ethylenically unsaturated monomer having a hydrocarbon ring combined with the compound represented by the general formula (1) include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl ( Examples include meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and styrene, and cyclohexyl (meth) acrylate because the cross-sectional shape of the colored layer after development is highly effective in heat treatment. , Dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable.

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. In the case of having an ethylenic double bond, the alkali-soluble resins, or the alkali-soluble resin and the polyfunctional monomer can form a cross-linked bond in the curing step of the resin composition at the time of producing the color filter. By combining with the compound represented by the general formula (1) used in the present invention, the film strength of the cured film is further improved and the development resistance is improved, and the thermal contraction of the cured film is suppressed, Excellent adhesion.
The method for introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method of introducing an ethylenic double bond into a side chain by adding a compound having both an epoxy group and an ethylenic double bond in the molecule, such as glycidyl (meth) acrylate, to the carboxyl group of the alkali-soluble resin Or by introducing a structural unit having a hydroxyl group into a copolymer, adding a compound having an isocyanate group and an ethylenic double bond in the molecule, and introducing an ethylenic double bond into the side chain. Etc.

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

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

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

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

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

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

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

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

When the ethylenically unsaturated bond equivalent in the case of having an ethylenically unsaturated group in the side chain of the alkali-soluble resin is combined with the compound represented by the general formula (1) used in the present invention, the film strength of the cured film is obtained. Is improved, the development resistance is improved, and it is preferable to be in the range of 100 to 2000, particularly in the range of 140 to 1500 from the viewpoint of obtaining the effect of excellent adhesion to the substrate. When the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Moreover, since the ratio of other structural units, such as the structural unit which has the said carboxy group, and the structural unit which has a hydrocarbon ring, can be relatively increased if it is 100 or more, it is excellent in developability and heat resistance. Yes. The compound represented by the general formula (1) used in the present invention is preferably used in combination with the content described above.
Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).

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

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

  The alkali-soluble resin used in the photosensitive colored resin composition for color filters may be used singly or in combination of two or more, and the content is not particularly limited. The alkali-soluble resin is preferably in the range of 5% by mass to 60% by mass and more preferably in the range of 10% by mass to 40% by mass with respect to the total solid content of the photosensitive colored resin composition for filters. When the content of the alkali-soluble resin is not less than the above lower limit value, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is not more than the above upper limit value, film roughness or lack of pattern can be caused during development. Can be suppressed.

[Photopolymerizable compound]
The photopolymerizable compound used in the photosensitive colored resin composition for a color filter is not particularly limited as long as it can be polymerized by the photoinitiator, and usually has two or more ethylenically unsaturated double bonds. It is preferable to use a polyfunctional (meth) acrylate having 2 or more acryloyl groups or methacryloyl groups.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include those described in JP2013-029832A.

  These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. When the photosensitive colored resin composition for color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Preferred are poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. Succinic acid modified product of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) ) Succinic acid modified product of acrylate, dipen Hexa (meth) acrylate are preferable.

Although there is no restriction | limiting in particular in content of the said polyfunctional monomer used in the photosensitive coloring resin composition for color filters, Preferably a polyfunctional monomer is 5 with respect to solid content whole quantity of the photosensitive coloring resin composition for color filters. It is in the range of mass% to 60 mass%, more preferably 10 mass% to 40 mass%. When the content of the polyfunctional monomer is not less than the above lower limit, photocuring proceeds sufficiently, and the exposed portion can suppress elution during development, and when the content of the polyfunctional monomer is not more than the above upper limit, alkali development Sex is enough.
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 (1) are excellent in curability and a remaining film ratio. From the viewpoint of improving electrical reliability, the content ratio of the compound represented by the general formula (1) is preferably 5 parts by mass or more, and further 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. Part or more, preferably 40 parts by weight or less, and more preferably 30 parts by weight 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. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, 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 solvents such as ethyl lactate and cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Tone solvents; glycol ether acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, 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, diethylene 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 solvents; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; Examples include organic solvents such as aromatic hydrocarbons such as xylene. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, as 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, And it is 1 or more types selected from the group which consists of 3-methoxybutyl acetate from the point of the solubility of another component, and the applicability | paintability.

  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 formed with high accuracy. The total amount of the photosensitive colored resin composition for color filters containing the solvent is usually 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. More preferably. When the content of the solvent is within the above range, the coating property can be excellent.

[Dispersant]
In the photosensitive colored resin composition of the present invention, the colorant is preferably used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer dispersant is preferable because it can be uniformly and finely dispersed.

  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 acid such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethylenimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxyls) Polyester, polyamide or ester-amide co-condensation with groups 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 them, a polymer dispersant containing a nitrogen atom in the main chain or side chain and having an amine value is preferable from the viewpoint that the colorant can be suitably dispersed and the dispersion stability is good. Among these, a polymer dispersant composed of a polymer containing a repeating unit having a tertiary amine is preferable from the viewpoint of good dispersibility, no precipitation of foreign matters when forming a coating film, and improvement of luminance and contrast.
The repeating unit having a tertiary amine is a site having an affinity for the colorant. The polymer dispersant made of a polymer containing a repeating unit having a tertiary amine usually contains a repeating unit that becomes a site having an affinity for a solvent. As a polymer containing a repeating unit having a tertiary amine, a block copolymer having a block part composed of a repeating unit having a tertiary amine and a block part having a solvent affinity is particularly preferable. It is preferable at the point which can form the coating film which is excellent in it and becomes high-intensity.

The repeating unit having a tertiary amine only needs to 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 among them, the structure represented by the following general formula (I) is preferable because the main chain skeleton is hardly thermally decomposed and has high heat resistance. Is more preferable.

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, Q is a divalent linking group, R ² 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 - 2 monovalent organic group represented by, ^{R 3} And R ⁴ each independently represents an optionally substituted chain or cyclic hydrocarbon group, or R ³ and R ⁴ are bonded to each other to form a cyclic structure, and R ⁵ and R ⁶ are Each independently represents 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, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (- R′—OR ″ —: R ′ and R ″ each independently represents an alkylene group) and combinations thereof. Among these, Q is a —COO— group or —CONH— from the viewpoint of heat resistance of the polymer obtained, solubility in propylene glycol monomethyl ether acetate (PGMEA) suitably used as a solvent, and a relatively inexpensive material. It is preferably a group.

The 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 —. The alkylene group having 1 to 8 carbon atoms may be linear or branched, for example, methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various hexylenes. Groups, various octylene groups and the like.
R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.
R ² is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility. Among them, R ² is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Groups are more preferred.

Examples of the cyclic structure formed by combining R ³ and R ^{4 in} the general formula (I) include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.

  Examples of the repeating unit represented by the general formula (I) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and other alkyl group-substituted amino groups. Examples include group-containing (meth) acrylates, alkyl group-substituted amino group-containing (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and the like. Of these, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.

  In the block part composed of repeating units having a tertiary amine, it is preferable that three or more structural units represented by the general formula (I) are included. Especially, from the point which improves a dispersibility and dispersion stability, it is preferable to contain 3-100 pieces, It is more preferable to contain 3-50 pieces, Furthermore, it is more preferable to contain 3-30 pieces.

A block having a block part (hereinafter sometimes referred to as A block) composed of a repeating unit having a tertiary amine and a block part having solvent affinity (hereinafter sometimes referred to as B block). As a block part having solvent affinity in the polymer, from the viewpoint of improving solvent affinity and improving dispersibility, the block unit does not have the structural unit represented by the general formula (I), 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 for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.
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. It is preferable that

(In 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 group having 2 to 18 carbon atoms. Group, an aralkyl group, an aryl group, a monovalent group represented by — [CH (R ⁹ ) —CH (R ¹⁰ ) —O] _x —R ¹¹ or — [(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, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, A monovalent group represented by an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹² , wherein R ¹² is a hydrogen atom or a linear, branched, or cyclic alkyl having 1 to 5 carbon atoms. 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 of the general formula (II) can be the same as Q in the general formula (I), and propylene glycol which is suitably used as the heat resistance and solvent of the obtained polymer. From the viewpoint of solubility in monomethyl ether acetate (PGMEA) and a relatively inexpensive material, A is preferably a —COO— group.

In R ^8, the alkyl group having 1 to 18 carbon atoms, linear, branched, or cyclic, e.g., methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl 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 group, 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 alkenyl groups include vinyl, allyl, propenyl, various butenyl, various hexenyl, various octenyl, various decenyl, various dodecenyl, various tetradecenyl, various hexadecenyl, various octadecenyl, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned.
Among these, R ⁸ is preferably a methyl group, various butyl groups, various hexyl groups, benzyl groups, cyclohexyl groups, or hydroxyethyl groups from the viewpoint 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. 6-24 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for carbon number of an aralkyl group, 7-14 are more preferable.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

R ¹¹ is a hydrogen atom or an optionally substituted 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 -CH2COOR ^{12, R 12} is a hydrogen atom or a number of 1 to 5 straight, branched, or cyclic alkyl group.
In the monovalent group represented by R ¹¹ , the substituent that may be included 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-compatible block part of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent-compatible block part is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher.
The glass transition temperature (Tg) of the solvent-affinity block part in the present invention can be calculated by the following formula. Similarly, the glass transition temperature of the colorant affinity block portion and the block copolymer can be calculated.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the solvent-affinity block portion. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. As the value of the homopolymer glass transition temperature (Tgi) of each monomer, the value of Polymer Handbook (3rd Edition) (by J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.

  What is necessary is just to adjust suitably the number of the structural units which comprise a solvent affinity block part in the range which a color material dispersibility improves. Among them, the number of structural units constituting the solvent affinity block part is 10 to 200 from the viewpoint that the solvent affinity part and the colorant affinity part effectively act and improve the dispersibility of the colorant. 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 may be included.
In the block copolymer used as the dispersant of the present invention, the ratio between the number m of the structural unit represented by the general formula (I) and the number n of other structural units constituting the solvent-affinity block unit 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 color material.

In particular, in the present invention, the dispersant is a polymer having a structure represented by the general formula (II) and having an amine value of 40 mgKOH / g to 120 mgKOH / g. It is preferable from the viewpoint of improving luminance and contrast without depositing foreign matters.
When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and is also excellent in alkali developability and solvent resolubility. In the present invention, the amine value of the dispersant is preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 110 mgKOH / g or less, more preferably 105 mgKOH / g or less.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of a sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if it is an amino group that forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so that the block copolymer itself used as the dispersant is itself The amine value of can be measured.

The acid value of the dispersant used in the present invention is preferably 1 mgKOH / g or more as a lower limit from the viewpoint of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2 mgKOH / g or more from the viewpoint of more excellent development residue suppression effect. In addition, the acid value of the dispersant used in the present invention is 18 mgKOH / g or less as the upper limit of the acid value of the dispersant from the viewpoint of preventing deterioration in development adhesion and solvent resolubility. preferable. Among these, the acid value of the dispersant is more preferably 16 mgKOH / g or less, and even more preferably 14 mgKOH / g or less, from the viewpoint of improving the development adhesion and the 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, and 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 resolubility are improved.

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

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

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

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

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

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

  In the block copolymer, the ratio m / n of the unit number m of the structural unit of the A block and the unit number n of the structural unit of the B block is in the range of 0.05 to 1.5. Is preferably in the range of 0.1 to 1.0 from the viewpoint of the 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 improving the colorant dispersibility and dispersion stability. More preferably, it is more preferably 3000-12000.
Here, the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC). The macromonomer, salt-type block copolymer, and graft copolymer that are the raw materials for the block copolymer are also subjected to the above conditions.

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

  As a specific example of a block copolymer having a block part composed of a repeating unit having a tertiary amine and a block part having a solvent affinity, for example, a block copolymer described in Japanese Patent No. 4911253 is used. It can be mentioned as a suitable thing.

  In the case of dispersing the colorant using a polymer containing a repeating unit having a tertiary amine as a dispersant, the polymer containing a repeating unit having the tertiary amine with respect to 100 parts by mass of the coloring material. Is preferably 15 parts by mass to 300 parts by mass, and more preferably 20 parts by mass to 250 parts by mass. If it is in the said range, it is excellent in the dispersibility and dispersion stability, and the effect which improves a contrast becomes high.

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

  The content in the case of using a dispersant is not particularly limited as long as it can uniformly disperse the coloring material. For example, the total solid content of the photosensitive colored resin composition for color filters is used. On the other hand, it can be used at 1% by mass to 40% by mass. Furthermore, it is preferable to mix | blend in 2 mass%-30 mass% with respect to the solid content whole quantity of the photosensitive coloring resin composition for color filters, and it is preferable to mix | blend especially in the ratio of 3 mass%-25 mass%. If it is more than the said lower limit, it is excellent in the storage stability of the dispersibility and dispersion stability of a color material, and the photosensitive coloring resin composition for color filters. Moreover, if it is below the said upper limit, developability will become favorable. In particular, when a colored layer having a high colorant 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 color filters. It is preferable to mix | blend in the ratio of 3 mass%-20 mass%.

[Optional components]
The photosensitive colored resin composition for color filters may contain various additives as necessary.
Examples of the additive include an antioxidant, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter. Can be mentioned.

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

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

The ratio of the mass (P) of the color material used in the present invention to the mass (V) of the solid content other than the color material (hereinafter sometimes referred to as “P / V ratio”) is the colored layer of the color filter. In this case, it is only necessary that the desired color can be produced, and it is not particularly limited, but is preferably in the range of 0.05 or more and 1.00 or less, and is in the range of 0.10 or more and 0.80 or less. More preferably, it is more preferably in the range of 0.15 or more and 0.75 or less, and particularly preferably in the range of 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 forming a desired color can be obtained, and further, the P / V ratio 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 ratio is high, so the P / V ratio is as high as 0.4 or more. The range can be set, and the luminance and color reproducibility can be improved.

In particular, in the case of a red colored resin composition, from the viewpoint of desired color development, the P / V ratio is preferably 0.50 or more, more preferably 0.60 or more, and still more preferably 0.00. It is preferable that it is 74 or more. Moreover, it is preferable that it is 1.0 or less.
In the case of a green colored resin composition, from the viewpoint of desired color development, the P / V ratio is preferably 0.46 or more, more preferably 0.56 or more, and still more preferably 0.00. It is preferable that it is 68 or more. Moreover, it is preferable that it is 1.0 or less.
Further, in the case of a blue colored resin composition, from the viewpoint of desired color development, the P / V ratio is preferably 0.24 or more, more preferably 0.34 or more, and still more preferably 0.00. It is preferable that it is 41 or more. Moreover, it is preferable that it is 1.0 or less. If it is more than the said lower limit, respectively, the color density of the photosensitive colored resin composition for color filters can be made high, and a color filter pixel can be made to have a higher color rendering and a lower film thickness. Moreover, if each is below an upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained.
Among them, the red colored resin composition and the green colored resin composition often need to increase the ratio of the color material in the solid content of the composition due to the difference in coloring power between the color and color material required for the color filter. In particular, in the green colored resin composition, it is often necessary to make the ratio of the pigment in the solid content of the composition highest 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 for 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 according to the present invention comprises a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, preferably a dispersant, and various additions used as desired. It is preferable from the point of improving the contrast that the coloring material can be uniformly dispersed in the solvent by the dispersant, and can be prepared by mixing using a known mixing means. .
As a method for preparing the resin composition, for example, (1) First, a color material and a dispersant are added to a solvent to prepare a color material dispersion, and the alkali-soluble resin, light, A method of mixing a polymerizable compound, a photoinitiator, and various additive components used as desired; (2) In a solvent, a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator (3) In a solvent, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a photoinitiator are optionally used. A method in which various additive components are added and mixed, and then a color material is added and dispersed; (4) A color material dispersion is prepared by adding a color material, a dispersant, and an alkali-soluble resin to a solvent. The dispersion is further mixed with an alkali-soluble resin, a solvent, and light. 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 that the aggregation of the coloring material can be effectively prevented and dispersed uniformly.

  The method for preparing the color material dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) A dispersant is mixed and stirred in advance 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 of mixing this with a coloring material and other components as necessary, and dispersing the mixture using a known stirrer or disperser; (2) Mixing and stirring a dispersant in a solvent to prepare a dispersant solution; A method of mixing a coloring material and, if necessary, an organic acid compound and, if necessary, other components and dispersing the mixture using a known stirrer or disperser; (3) mixing and stirring a dispersant in a solvent. Then, the dispersant solution is prepared, then the colorant and other components are mixed as necessary, and the mixture is made into a dispersion using a known stirrer or disperser, and then an organic acid compound is added as necessary. The method etc. are mentioned.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibrating ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

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

II. Color filter The color filter according to the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, and 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 the 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 part 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a colored layer made of a cured product of the photosensitive colored resin composition for color filters according to the present invention.
The colored layer is usually formed in an opening of a light shielding part on a transparent substrate, which will be described later, and is usually composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, etc. of the photosensitive colored resin composition for a color filter, but is usually preferably in the range of 1 μm to 5 μm. .

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

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, usually, the developer is washed and the cured coating film of the photosensitive colored resin composition for color filter is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

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

  The thickness of the light shielding part is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and is set to about 0.5 μm to 2 μm in the case where a black pigment is dispersed or dissolved in a binder resin. Is 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 a general color filter can be used. Specifically, transparent flexible rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible flexible materials such as transparent resin films, optical resin plates, and flexible glasses. Materials.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention is one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, and the like are formed in addition to the transparent substrate, the light shielding portion, and the colored layer. May be.

III. Display Device A display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device and an organic light emitting display device.

[Liquid Crystal Display]
The liquid crystal display device includes the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic 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.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

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

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

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

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

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
The structure of the obtained compound was determined by 1H- and 13C-NMR spectra measured using a nuclear magnetic resonance apparatus (Bruker Biospin, AVANCE III HD 500 MHz), and a liquid chromatograph mass spectrometer (Shimadzu Corporation, LC- It was confirmed by mass spectrometry using 30A, Bruker Daltonics, MICROTOFQ2).

(Synthesis Example 1: Synthesis of Compound 2)
Dissolve 56.2 g of N-ethylcarbazole in 800 ml of chloroform, add 128.6 g of aluminum chloride and stir at 0 ° C., and then add a solution of 55.0 g of 3-cyclohexylpropionyl chloride in 300 ml of chloroform over 2 hours. And dripped. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was stirred again at 0 ° C., and a solution prepared by dissolving 49.7 g of capryloyl chloride in 200 ml of chloroform was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 3 hours. The reaction solution was poured into 1800 g of ice water and extracted with 2000 ml of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 114.9 g of compound (2-A) (yield 86.9). %).
Next, the compound (2-B) which is a precursor of the compound 2 was synthesize | combined from the obtained compound (2-A) as follows. To a solution of 88.5 g of compound (2-A), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid, 59.3 g of tert-butyl nitrite was added dropwise over 1 hour with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give compound (2-B) 93 0.8 g was obtained (yield 94.1%).
Next, Compound 2 was synthesized as follows using the obtained compound (2-B). When 44.6 g of compound (2-B) was stirred in 500 ml of ethyl acetate, 26.4 g of acetic anhydride and 15.6 g of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 ml of ice water, the product was extracted with ethyl acetate, the organic layer was washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered, and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to synthesize 46.7 g of compound 2 represented by the following chemical formula. (Yield 90.0%).

(Synthesis Example 2: Synthesis of Compound 6)
In Synthesis Example 1, using N-ethylcarbazole as a starting material, 3-cyclohexylpropionyl chloride was changed to an equimolar amount of 2- (4,6-dimethyl-2-pyrimidinylthio) -acetyl chloride, and capryloyl chloride was changed to lauroyl. Compound 6 represented by the following chemical formula was synthesized in the same manner as in Synthesis Example 1 except that the molar amount of chloride was changed to an equimolar amount.

(Comparative Synthesis Example 1: Synthesis of Comparative Compound A)
82.1 g of N-ethyl 1,8-nitrocarbazole was dissolved in 800 ml of chloroform, and 128.6 g of aluminum chloride was further added. The mixture was stirred at 0 ° C., and 60.5 g of 2- (cyclohexyloxy) acetyl chloride was added to 300 ml of chloroform. The solution dissolved in 2 was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 4 hours. The reaction solution was stirred again at 0 ° C., and a solution prepared by dissolving 36.8 g of pentanoyl chloride in 200 ml of chloroform was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 25 ° C. for 3 hours. The reaction solution was poured into 1800 g of ice water and extracted with 2000 ml of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 127.4 g of a comparative compound (AA) (yield: 86. 9%).
Next, the comparative compound (AB) was synthesized from the obtained comparative compound (AA) as follows. When dissolved in a mixed solution of 98.1 g of the comparative compound (AA), 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid, 18.9 g of hydroxylamine was added dropwise over 1 hour with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give a comparative compound (AB). 88.8g was obtained (yield 85.7%).
Next, Comparative Compound A was synthesized as follows using the obtained Comparative Compound (AB). When 40.1 g of the comparative compound (AB) was stirred in 500 ml of ethyl acetate, acetic anhydride and sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 ml of ice water, the product was extracted with ethyl acetate, the organic layer was washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered, and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to synthesize 48.4 g of Comparative Compound A represented by the following chemical formula (yield 90.0%).

(Comparative Synthesis Example 2: Synthesis of Comparative Compound B)
In Comparative Synthesis Example 1, except that the starting material was changed to an equimolar amount of N-propyl 1-nitrocarbazole and 2- (cyclohexyloxy) acetyl chloride was changed to an equimolar amount of 2- (cyclohexylthio) acetyl chloride. Comparative compound B represented by the following chemical formula was synthesized in the same manner as in Comparative Synthesis Example 1. (Yield 90.5%)

(Synthesis Example 3: Production of Dispersant (Block Copolymer A))
Add 250 parts by weight of THF and 0.6 parts by weight of lithium chloride to a 500 mL round bottom 4-neck separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and perform sufficient nitrogen replacement. It was. After cooling the reaction flask to −60 ° C., 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine and 1.0 part by mass of methyl isobutyrate were injected using a syringe. B block monomer 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by weight, 2-hydroxyethyl methacrylate (HEMA) 18.7 parts by weight, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by weight, methacryl 13.7 parts by mass of n-butyl acid (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 the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, diluted with PGMEA to obtain a solid content solution of 30% by mass. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C., and the mixture was allowed to react for 7 hours. The structural unit derived from EEMA was deprotected to obtain a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, purified by filtration and vacuum drying, and a structural unit derived from a block containing a structural unit represented by the general formula (I) and a carboxy group-containing monomer A block copolymer A (acid value: 8 mgKOH / g, Tg: 38 ° C.) containing a B block having solvophilic properties. The block copolymer A-1 thus obtained was confirmed by GPC (gel permeation chromatography), and 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 in a nitrogen stream. did. After completion of dropping, the mixture was further heated at 100 ° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.
Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol are added to the obtained polymer solution and heated at 110 ° C. for 10 hours to react. Air was bubbled through the solution. The obtained alkali-soluble resin A is a resin in which a side chain having an ethylenic double bond is introduced into the main chain formed by copolymerization of BzMA, MMA, and MAA using GMA, and has a solid content of 42.6 mass. %, Acid value 74 mgKOH / g, and weight average molecular weight 12000. The weight average molecular weight was measured with Shodex GPC System-21H (Polystyrene) using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070.

(Synthesis Example 5: Synthesis of alkali-soluble resin B solution)
In Synthesis Example 4, 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. The solid content was 42.6% by mass, the acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

(Synthesis Example 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 in Synthesis Example 4. The solid content was 42.6% by mass, the acid value was 74 mgKOH / g, and the weight average molecular weight was 12,000.

(Synthesis Example 7: Synthesis of Color 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 (“trade name: Takibaine # 1500” manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, basicity 83.5 mass%, alumina content 23.5 mass%) in 200 ml of water The mixture was stirred at 80 ° C. to prepare a polyaluminum chloride aqueous solution. The prepared polyaluminum chloride aqueous solution was added dropwise to the dye solution at 80 ° C. over 15 minutes, and further stirred at 80 ° C. for 1 hour. The formed precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 6.30 g (yield 96.2%) of a metal lake color material A of a rhodamine acid dye.

Example 1
(1) Production of colorant dispersion 1
13.3 parts by mass of the block copolymer A of Synthesis Example 3 as a dispersant and C.I. I. 13.0 parts by mass of Pigment Green 59 (PG59, manufactured by FASTOGEN GREEN C100 DIC), 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 , 100 parts by weight of 2.0 mm zirconia beads are put into a mayonnaise bin, shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a preliminary crushing, and then the 2.0 mm zirconia beads are taken out, 200 parts by mass of zirconia beads having a particle size of 0.1 mm was added, and similarly, this dispersion was dispersed for 4 hours with a paint shaker to obtain a colorant dispersion 1.

(2) Production of photosensitive colored resin composition 1 for color filter 287.0 parts by mass of the colorant dispersion 1 obtained in the above (1), and 25. of the alkali-soluble resin A solution obtained in Synthesis Example 4. 67 parts by mass, 20.20 parts by mass of a photopolymerizable compound (trade name Aronix M-520D, manufactured by Toagosei Co., Ltd.), 5.1 parts by mass of Compound 2 of Synthesis Example 1 as a photoinitiator, and PGMEA 84.63 mass parts was added, and the photosensitive colored resin composition 1 for color filters was obtained.

(Examples 2-11, Comparative Examples 1-6)
In Example 1, instead of using 5.1 parts by mass of Compound 2 of Synthesis Example 1 as the photoinitiator, Example 1 was used except that the photoinitiator shown in Table 1 was used in the amount shown in Table 1. In the same manner, photosensitive colored resin compositions 2 to 11 for color filters and photosensitive colored resin compositions 1 to 6 for comparative color filters were obtained.

Example 12
In Example 3, C.I. I. Instead of using CI Pigment Green 59 (PG59), C.I. I. Except having used pigment red 254 (PR254), it carried out similarly to Example 3, and obtained the photosensitive colored resin composition 12 for color filters.

(Example 13)
In Example 1, C.I. I. A photosensitive colored resin composition 13 for a color filter was obtained in the same manner as in Example 1 except that Acid Red 289 (AR289) (xanthene dye) was used instead of Pigment Green 59 (PG59).

(Comparative Example 7)
In Comparative Example 1, C.I. I. A photosensitive colored resin composition 7 for a comparative color filter was obtained in the same manner as in Comparative Example 1 except that Acid Red 289 (AR289) (xanthene dye) was used instead of Pigment Green 59 (PG59).

(Example 14)
In Example 1, C.I. I. A photosensitive colored resin composition 14 for a color filter was obtained in the same manner as in Example 1 except that the coloring material A obtained in Synthesis Example 7 was used instead of using Pigment Green 59 (PG59).

(Example 15)
In Example 7, C.I. I. Instead of using Pigment Green 59 (PG59), the colorant A obtained in Synthesis Example 7 was used, and an alkali-soluble resin B solution was used instead of the alkali-soluble resin A solution. A photosensitive colored resin composition 15 for a color filter was obtained.

(Example 16)
In Example 7, C.I. I. Instead of using Pigment Green 59 (PG59), the colorant A obtained in Synthesis Example 7 was used, and an alkali-soluble resin C solution was used instead of using the alkali-soluble resin A solution. A photosensitive colored resin composition 16 for color filters was obtained.

[Evaluation]
Evaluation of the following photosensitive resin composition was performed after storing the photosensitive colored resin composition obtained in each Example and each Comparative Example for 12 hours in a refrigerator maintained at 4 ° C.
(1) Residual film ratio The photosensitive colored resin composition obtained in each Example and each Comparative Example was applied onto a glass substrate (NH Techno Glass Co., Ltd., “NA35”) using a spin coater. Then, it was dried at 80 ° C. for 3 minutes using a hot plate to form a coating film on the glass substrate. The whole surface was irradiated with 60 mJ / cm ² of ultraviolet light using an ultrahigh pressure mercury lamp without passing through a photomask to form a post-exposure coating film. Next, spin development was performed using a 0.05 wt% potassium hydroxide aqueous solution as a developer, and the resulting solution was indirectly developed for 60 seconds and then washed with pure water to form a post-development coating film. Thereafter, it was post-baked 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 the coating film, the film thickness after exposure (E), the film thickness after development (D), and the film thickness after post-baking (B) are stylus profiler P-16 (manufactured by KLA-Tencor). The film thickness after development (D) / the film thickness after exposure (E) was calculated.
The film thickness after development (D) / film thickness after exposure (E) is 95% or more, which is a range suitable for actual use.

(2) Variation in line width Using a spin coater, the photosensitive colored resin composition obtained in each example and each comparative example was placed on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.). After applying the cured coating film so as to have 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 the glass substrate. By exposing the coating film with ultraviolet light 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, a post-exposure coating film is formed on the glass substrate, Next, 0.05 wt% aqueous potassium hydroxide solution is spin-developed as a developing solution, the developing solution is subjected to an indirect solution for 60 seconds and then washed with pure water, followed by post-processing for 25 minutes in a 230 ° C. clean oven. Baking was performed to form a fine line pattern. Of the formed fine line pattern, the width of the fine line pattern of the portion where the opening width of the chromium mask at the time of exposure corresponds to 90 μm is measured with an optical microscope, and the five portions where the opening width of the chromium mask in the substrate is 90 μm are measured, The variation in line width was evaluated.
<Evaluation criteria>
A: Variation within ± 0.1 μm B: Variation over ± 0.1 μm within ± 0.3 μm C: Variation over ± 0.3 μm within ± 0.5 μm

(3) Line width increase / decrease rate The photosensitive colored resin composition obtained in each Example and each Comparative Example was formed on a glass substrate (“NA Techno Glass Co., Ltd.,“ NA35 ”) using a spin coater. After applying the cured coating film so as to have 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 the glass substrate. By exposing the coating film with ultraviolet light 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, a post-exposure coating film is formed on the glass substrate, Next, 0.05 wt% aqueous potassium hydroxide solution is spin-developed as a developing solution, the developing solution is subjected to an indirect solution for 60 seconds and then washed with pure water, followed by post-processing for 25 minutes in a 230 ° C. clean oven. Baking was performed to form a fine line pattern. Of the formed fine line patterns, the width of the fine line pattern at the portion where the opening width of the chrome mask at the time of exposure corresponds to 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 ± 3% of target line width B: Over ± 3% of target line width Within ± 5% C: Over ± 5% of target line width Within ± 10%

(4) Electrical reliability A pair of ITO substrates A and B, in which ITO (indium tin oxide) electrodes are provided on the surface of a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.), is prepared. The photosensitive colored resin composition obtained in each Example and each Comparative Example was applied to the surface of the ITO substrate A with a spin coater and dried on an 80 ° C. hot plate for 3 minutes to form a coating film. Next, the coating film was irradiated with ultraviolet rays with a 60 mJ / cm ² exposure machine through a photomask using an ultra-high pressure mercury lamp. After the irradiation, the substrate was developed with a 0.05 wt% aqueous potassium hydroxide solution for 1 minute with a spin developing machine, then 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 produce a colored layer arranged in a pattern on the substrate.
(Production of liquid crystal cell)
In addition, the ITO substrate B is prepared, 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 colored layer arranged in the pattern is formed on the ITO. The colored layer surface of the substrate A was placed oppositely and heated in an oven at 180 ° C. for 2 hours. Liquid crystals (MLC Japan Co., Ltd., MLC-6846-000) are injected into the empty cell formed between the above-mentioned pressure-bonded substrates, and the periphery is sealed with a UV curable sealant, for measuring 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 measurement conditions.
(Voltage holding ratio)
Using the liquid crystal cell obtained above, ITO substrates A and B 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 using a voltage holding ratio measuring system (manufactured by Toyo Technica Co., Ltd., VHR-1A type).
(Evaluation criteria)
A: Voltage holding ratio is 90% or more (liquid crystal display stability is extremely 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 a liquid crystal display failure)
A and B or more are within the practical range.

Abbreviations in the table are as follows.
OXE-1: Oxime ester photoinitiator (trade name Irgacure OXE-01, manufactured by BASF)
PBG304: Oxime ester photoinitiator (TR-PBG-304, Changzhou Power Electronics New Materials Co., Ltd.)
Irg369: α-aminoketone photoinitiator (Irgacure 369, manufactured by BASF)
Irg907: α-aminoketone photoinitiator (Irgacure 907, manufactured by BASF)
Mercapto series: Mercapto chain transfer agent (2-mercaptobenzothiazole, manufactured by Tokyo Chemical Industry Co., Ltd.)
Biimidazole series: Biimidazole series photoinitiator (HABI, manufactured by Kurokin Kasei)
DETX: thioxanthone photoinitiator (DOUBLECURE DETX, manufactured by Double Bond Chemical)
Irg819: Acylphosphine oxide photoinitiator (Irgacure 819, manufactured by BASF)

(5) Solvent Solubility Test of Dioxime Ester Initiator Compound 2 and Compound 6, Comparative Compound A and Comparative Compound Represented by General Formula (1) with respect to a total of 10 g of solvents at the ratio shown in Table 2 0.1 g of each compound B was added and stirred at 25 ° C. for 30 minutes, and the dissolution state was visually confirmed. Then, after storing for 12 hours in a refrigerator maintained at 4 ° C., the dissolution state of each initiator was again visually confirmed.
Solvent 1: PGMEA
Solvent 2: Diethylene glycol ethyl methyl ether Solvent 3: 3-methoxy-3-methyl-1-butyl acetate <Evaluation criteria>
A: No precipitation of initiator after refrigerated storage B: Precipitation occurs after refrigerated storage C: Initiator does not dissolve and precipitates after stirring for 30 minutes at 25 ° C

<Summary of results>
The photosensitive colored resin compositions of Examples 1 to 16 containing the compound represented by the general formula (1) as a photoinitiator have excellent curability even when the colorant concentration is high, and the remaining film It was revealed that the photosensitive colored resin composition has a high rate, a small variation in line width, and a low sensitivity variation even after refrigerated storage. Moreover, the photosensitive colored resin composition of Examples 1-16 containing the compound represented by the said General formula (1) as a photoinitiator is excellent in evaluation of the said voltage retention, and has the reliability of a color filter. The improvement effect was also revealed. When a dye is used as a coloring material, there is a concern that the reliability is lowered because it is easy to bleed out. However, according to the present invention, the oozing out of the dye is suppressed as compared with the conventional case, and the reliability of the color filter is improved. (Comparison between Example 13 and Comparative Example 7)
In addition, as a photoinitiator, the compound represented by the general formula (1) is added to an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, In addition, it has been clarified that, when a combination of at least one of mercapto chain transfer agents and a mercapto chain transfer agent is used, the ability to form a fine line pattern according to the design of the mask line width is improved when a fine line pattern is formed (Examples). 1 and comparison with Examples 2-11).
On the other hand, in Comparative Example 1 using a monooxime ester-based initiator as a photoinitiator, the remaining film ratio was low, the line width variation was large, and the voltage holding ratio was inferior. In Comparative Examples 2 and 3 using an α-aminoketone photoinitiator as a photoinitiator, the remaining film ratio was low and the voltage holding ratio was also inferior. In Comparative Example 4 in which the α-aminoketone photoinitiator was combined with the monooxime ester initiator as the photoinitiator, the variation in line width was improved, but the remaining film ratio was low and the voltage holding ratio was also inferior. .
Moreover, even if it is a dioxime ester type initiator (oxime ester compound which has two oxime ester groups in a molecule | numerator) as a photoinitiator, it has a structure different from the compound represented by the said General formula (1). In Comparative Examples 5 and 6 using the oxime ester-based initiator, it was revealed that the line width variation was greatly inferior after refrigerated storage.

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

Claims (5)

Containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent;
The photosensitive coloring resin composition for color filters in which the said photoinitiator contains the compound represented by following General formula (1).
(In General Formula (1), W ¹ and W ² each independently represent a carbonyl bond (—CO—) or a single bond, and at least one of W ¹ and W ² is a carbonyl bond (—CO—). R ^a is an alkyl group having 2 to 6 carbon atoms, R ^b is an alkyl group having 4 to 10 carbon atoms, R ^c includes at least a hydrocarbon ring or a heterocyclic ring, and further has 1 to 4 carbon atoms. An alkylene chain, a thioether bond (—S—), an ether bond (—O—), and a carbonyl bond (—CO—), which may contain at least one divalent linking group. R ^b and R ^c are different from each other, and R ^d and R ^e are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group.)   The photoinitiator is further at least one selected from α-aminoketone photoinitiators, biimidazole photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents. The photosensitive coloring resin composition for color filters of Claim 1 containing this. The dispersant according to claim 1 or 2, further comprising a dispersant, wherein the dispersant includes a polymer having a structure represented by the following general formula (I) and an amine value of 40 mgKOH / g or more and 120 mgKOH / g or less. Photosensitive color resin composition for color filters.
(In 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, — [CH (R ⁵ ) A divalent organic group represented by —CH (R ⁶ ) —O] _x —CH (R ⁵ ) —CH (R ⁶ ) — or — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y —. , 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 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. )   4. A color filter for color filter according to claim 1, wherein the color filter comprises at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a color filter for photosensitive coloring according to claim 1. A color filter comprising a colored layer made of a cured product of a resin composition.   A display device comprising the color filter according to claim 4.