TW201818154A - Photosensitive color resin composition for color filter, color filter and display device - Google Patents

Abstract

The present invention provides a photosensitive color resin composition for a color filter, which can form an improved luminance color layer and is high in sensitivity. The photosensitive color resin composition for a color layer includes a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, wherein the photoinitiator contains an oxime ester compound represented by the following general formula (1): (the symbols in the general formula (1) are as described in the description.).

Description

 Photosensitive colored resin composition for color filter, color filter, and display device  

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 (especially the development of mobile PCs for mobile use), the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, and tablets) has also increased, showing an ever-expanding market for liquid crystal displays. Further, recently, an organic light-emitting display device such as an organic EL display which uses self-luminous light and has high visibility has also become a new-generation image display device which has attracted attention. The performance of such image display devices is strongly eager for further high image quality and reduced power consumption.

These liquid crystal display devices and organic light-emitting display devices use color filters. For example, the color image formation of the liquid crystal display device is directly colored by the light passing through the color filter to form the color of each pixel constituting the color filter, and then combined with the color light to form a color image. In the case of the light source at this time, in addition to the conventional cold cathode tube, there are cases in which an organic light-emitting element that emits white light or a white light-emitting inorganic light-emitting element is used. Further, in the organic light-emitting display device, a color filter is used for color adjustment or the like.

In recent years, there has been a demand for power saving of an image display device, and in order to improve the utilization efficiency of the backlight, a color filter is required to have high luminance. In particular, it will become a big issue for mobile displays (mobile phones, smart phones, tablets).

Here, the color filter generally includes a substrate, a coloring layer formed on the substrate and composed of red, green, and blue primary coloring patterns, and a light blocking portion formed on the substrate so as to distinguish the respective colored patterns.

In the coloring layer forming method of the color filter, for example, a coloring resin composition is added to a color material dispersion liquid in which a color material is dispersed by a dispersing agent or the like, and a binder resin, a photopolymerizable compound, and a photoinitiator are added to form a colored resin composition. After being applied to a glass substrate, dried, and then exposed using a photomask, a coloring pattern is formed by performing development, and a coloring layer is formed by fixing the pattern by heating. These steps are repeated for each color to form a color filter.

Under the foreseeable high-luminance requirement of the color filter, by increasing the concentration of the color material of the colored layer of the color filter, it is relatively difficult to cause relatively few components necessary for photopolymerization, resulting in difficulty in patterning. Further, in order to improve the color filter productivity, it is required to reduce the cumulative exposure amount necessary for patterning, but how to ensure the hardenability necessary for patterning becomes a big problem.

In order to obtain a method capable of achieving a highly sensitive colored resin composition, an oxime ester photoinitiator has been proposed. For example, Patent Document 1 proposes an oxime ester compound having a specific structure and a carbazole skeleton. Further, Patent Document 2 proposes an oxime ester oxime compound having a specific structure in which an oxime ester group is bonded to a fluorene skeleton without a carbonyl group. Further, Patent Document 3 proposes an oxime ester compound containing a diphenyl sulfide skeleton or a carbazole skeleton, and the oxime ester group having a specific substituent of a cycloalkyl group.

 [Previous Technical Literature]    [Patent Literature]  

Patent Document 1: Japanese Patent No. 3992725

Patent Document 2: Japanese Patent Laid-Open Publication No. 2015-523318

Patent Document 3: Chinese Patent Application Publication No. 103293855

However, conventional colored resin compositions using an oxime ester photoinitiator tend to have insufficient brightness. In particular, a conventional high-sensitivity oxime ester photoinitiator tends to have a low luminance. On the other hand, the sensitivity of the oxime ester photoinitiator which is relatively easy to be a good luminance is low, and the influence on the sensitivity and the luminance caused by the oxime ester photoinitiator is like a sawing relationship. Therefore, it is desired to achieve a high-sensitivity, colored resin composition capable of forming a higher-luminance colored layer.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a photosensitive colored resin composition for a color filter which can form a colored layer having a raised luminance and which has a good sensitivity, and has sensitivity for use with the color filter. A color filter in which a colored layer is formed by a colored resin composition, and a display device using the color filter.

The photosensitive colored resin composition for a color filter of the present invention contains a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent; wherein the photoinitiator contains the following general formula; (1) The oxime ester compound shown: [Chemical Formula 1] General Formula (1)

(In general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group; and R ^c may also contain a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond ( a hydrocarbon group of at least one divalent linking group selected from -CO-); a Z-based hydrogen atom or -(C=O)R ^d ; and a R ^d system may further contain at least one selected from the group consisting of an oxygen atom and a sulfur atom a hydrocarbon group or a heterocyclic group which does not contain a nitrogen atom and which contains at least one selected from the group consisting of an oxygen atom and a sulfur atom; and R ^e is a hydrocarbon group having 1 to 10 carbon atoms.

The color filter of the present invention includes at least a substrate and a coloring layer provided on the substrate; wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition for a color filter of the present invention. The colored layer formed.

Furthermore, the present invention provides a display device including the above-described color filter of the present invention.

According to the present invention, there is provided a photosensitive coloring resin composition for a color filter which can form a coloring layer having a raised luminance and which has a good sensitivity, and has a coloring layer formed using the photosensitive colored resin composition for the color filter. a color filter, and a display device using the color filter.

1‧‧‧Substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧Anti-substrate

30‧‧‧Liquid layer

40‧‧‧Liquid crystal display device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧ hole injection layer

73‧‧‧ hole transport layer

74‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

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

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

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

Hereinafter, the photosensitive colored resin composition for a color filter of the present invention, a color filter, and a display device will be described in detail in order.

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

In the present invention, the "(meth)acrylyl group" means an acryl group and a methacryl group, respectively, and the "(meth)acrylate" means an acrylate and a methacrylate, respectively.

In this specification, unless otherwise stated, the chromaticity coordinates x and y refer to the XYZ color system of JIS Z8701 which uses the C light source for color measurement.

 I. Photosensitive colored resin composition for color filter  

The photosensitive colored resin composition for a color filter of the present invention contains a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent; wherein the photoinitiator contains the following general formula; (1) The oxime ester compound shown: [Chemical 2] General formula (1)

(In general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group; and R ^c may also contain a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond ( a hydrocarbon group of at least one divalent linking group selected from -CO-); a Z-based hydrogen atom or -(C=O)R ^d ; and a R ^d system may further contain at least one selected from the group consisting of an oxygen atom and a sulfur atom a hydrocarbon group or a heterocyclic group which does not contain a nitrogen atom and which contains at least one selected from the group consisting of an oxygen atom and a sulfur atom; and R ^e is a hydrocarbon group having 1 to 10 carbon atoms.

In the photosensitive colored resin composition for a color filter of the present invention, the oxime ester compound represented by the above general formula (1) is used as a photoinitiator to form a coloring layer having a raised luminance, and has a good sensitivity. Further, the photosensitive colored resin composition for a color filter of the present invention has an advantage of suppressing the occurrence of development residue, and when the colored layer is patterned, the desired minute pores can be easily formed on the colored layer at the same time.

In the photosensitive coloring resin composition for a color filter of the present invention, the oxime ester compound represented by the above formula (1) is used as a photoinitiator, and the effect of the above-described effects is not clear, but it can be estimated as follows.

The luminance of the colored layer is lowered, and the coloring phenomenon caused by the reaction residue of the photoinitiator may be one of the causes. The oxime ester-based initiator which is high in sensitivity but has insufficient coloration of the colored layer is presumed to have a structure such as a carbazole skeleton and the like, and it is easy to cause the reaction residue of the photoinitiator to be colored. On the other hand, the oxime ester compound represented by the above general formula (1) used in the present invention has a structure which is less likely to cause coloring of the reaction residue and has a high transmittance, and thus can suppress the coloring layer due to the reaction residue. By coloring, it is considered that a colored layer having a raised luminance can be formed.

Further, the oxime ester compound represented by the above general formula (1) used in the present invention has an anthracene skeleton and has an oxime ester group via a carbonyl group, so that the conjugated system of the structure does not adversely affect the luminance by The structure of the absorption intensity at the time of exposure is improved, and the estimated sensitivity is good. Further, the oxime ester compound represented by the above general formula (1) used in the present invention is a photopolymerization initiator which generates a methyl radical, compared to an alkyl radical or an aromatic radical which generates a large carbon number. The photopolymerization initiator is considered to have a good sensitivity because the radical moves rapidly.

In addition, the photosensitive colored resin composition for a color filter of the present invention is an oxime ester compound represented by the above formula (1) or a reactive residue thereof, and has a high affinity for an aqueous alkali solution during alkali development. It is presumed that the development residue can be easily suppressed.

Further, in the photosensitive colored resin composition for a color filter of the present invention, when the colored layer is patterned, the desired fine pores can be easily formed on the colored layer at the same time. When a coloring layer is formed to use a higher sensitivity photoinitiator, after generating a radical, the radical will move to the unexposed portion, causing the inside of the exposed portion to retain the shape of an unexposed portion, and is not exposed. It is difficult to form a non-trembling state in the peripheral portion of the part. Therefore, in the conventional photosensitive resin composition, when a high-sensitivity photoinitiator capable of forming a fine line pattern is used, even if the linearity of the fine line pattern is good, it is difficult to form minute pores. Further, in Comparative Example 2 to be described later, when a photoinitiator having a low sensitivity is used, even if micropores can be formed, there is a problem that the residual film ratio is lowered. On the other hand, in the photosensitive colored resin composition for a color filter of the present invention, micropores can be easily formed by using the oxime ester compound represented by the above general formula (1). In particular, by adjusting the content of the photoinitiator and the content of the antioxidant used in combination, it is possible to more easily form fine pores of a good shape. The photosensitive colored resin composition for a color filter of the present invention can be easily formed into a desired color on a colored layer, and is therefore suitable for forming a reflective color filter, for example, to form a color on a TFT substrate. The layer, and at the same time, the use of a common through hole in the colored layer.

Further, the oxime ester compound represented by the above general formula (1) used in the present invention has an oxime ester group via a carbonyl group on the fluorene skeleton, whereby the oxime ester is bonded to the oxime skeleton in comparison with the carbonyl group. In the oxime ester compound having a structure, since the crystallinity is lowered, solvent solubility and solvent resolubility are improved, and compatibility with other components becomes good. By using solvent-solubilizing agents and solvent re-solubility and light-initiating agents which are improved in compatibility with other components, the linearity of the fine line pattern can be improved, or the micro-hole tremor can be easily suppressed.

Further, since the oxime ester compound represented by the above general formula (1) has a high thermal decomposition temperature, generation of outgassing during heating of the coating film can be suppressed. Therefore, the reliability of the photoresist is high. For example, when another layer such as a conductive film is further laminated on the coating film, it is possible to suppress the layer of the laminated layer from being damaged by the outgas.

The photosensitive colored resin composition for a color filter of the present invention contains a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may be within a range that does not impair the effects of the present invention. It further contains other ingredients.

Hereinafter, each component of the colored resin composition of the present invention will be described in detail from the above-mentioned photoinitiator which is characteristic of the present invention.

 [light initiator]    <An oxime ester compound represented by the general formula (1)>  

The photoinitiator used in the present invention contains the oxime ester compound represented by the above general formula (1).

In the above general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group. From the viewpoints of solvent solubility and compatibility with other components, R ^a and R ^{b are} preferably each independently an alkyl group. The alkyl group may be any of a straight chain, a branched chain, a cyclic group, or a combination of the selected alkyl groups. The alkyl group may, for example, be an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, cyclopentyl group or methyl ring. a pentyl group, a cyclopentylmethyl group, a cyclohexyl group, etc., preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 4 carbon atoms, and a linear alkyl group having a carbon number of 2 to 4 base.

In the above general formula (1), the R ^c system may further contain at least one divalent linking group selected from the group consisting of a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-). Hydrocarbyl group.

The hydrocarbon group of the above R ^c may, for example, be an alkyl group, an alkenyl group, an aryl group or an aralkyl group. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain, and may be a combination of a linear chain and a cyclic chain. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group and cyclopentyl group. , cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylethyl, Basis A group, a dicyclopentyl group, an adamantyl group, a lower alkyl group substituted adamantyl group or the like. The above alkenyl group may be any of a linear chain, a branched chain, and a cyclic chain, and examples thereof include a vinyl group, an allyl group, and an allyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The aralkyl group may, for example, be a benzyl group, a phenethyl group, a naphthylmethyl group or a naphthylethyl group. The hydrocarbon group of R ^c is particularly preferably a hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms. It is an alkyl group having 1 to 10 carbon atoms. Further, when micropores are formed in the colored layer, the hydrocarbon group of R ^c preferably has 2 or more carbon atoms from the viewpoint of enhancing the shape of the micropores. Further, from the viewpoint of solvent solubility and compatibility, the hydrocarbon group of R ^c preferably has a structure of a cyclic or linear alkyl group such as a cyclopentylmethyl group or a cyclohexylmethyl group.

Further, in the above R ^c , since the hydrocarbon group contains the divalent linking group, solvent solubility and compatibility can be improved. The above-mentioned divalent linking group is preferably a thioether bond (-S-) or an ether bond (-O-) from the viewpoint of improving solvent solubility. In the above R ^c , when the hydrocarbon group contains the divalent linking group, the hydrocarbon group may be bonded to a carbon atom of the oxime ester group via the divalent linking group, and the carbon atom of the hydrocarbon group may be directly bonded to The carbon atom of the oxime ester group. In the above R ^c , when the hydrocarbon group contains the divalent linking group and the carbon atom of the hydrocarbon group is directly bonded to a carbon atom of the oxime ester group, the above R ^{c is} derived from the hydrocarbon group. The case of connecting the base of the base phase bond. The group in which the hydrocarbon group is bonded to each other by the above-mentioned divalent linking group may, for example, be a structure containing a thioether bond (-S-) such as an alkylthioalkyl group such as a methylthiomethyl group or an arylsulfanyl group; a structure containing an ether bond (-O-) such as an oxymethyl group, a methoxycyclohexyl group, an alkoxyalkyl group or an aryloxyalkyl group; an ethyl hydrazine methyl group, a benzamidine methyl group, a deuterated alkyl group or the like The structure of a carbonyl bond (-CO-), etc.

In the above general formula (1), a Z-based hydrogen atom or -(C=O)R ^d ; R ^d may contain at least one hydrocarbon group selected from an oxygen atom and a sulfur atom, or may contain no nitrogen atom but contain At least one heterocyclic group selected from an oxygen atom and a sulfur atom.

R ^d above may be contained at least one kind of selected from a hydrocarbon and an oxygen atom a sulfur atom, can be based for example as: hydrocarbon group described above R ^c, R ^c is a hydrocarbon group described above, the system further comprising an ether bond a group of at least one linking group selected from the group consisting of a linking group containing an oxygen atom such as a carbonyl bond (-CO-) and a linking group containing a sulfur atom such as a thioether bond (-S-). It is a hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and particularly preferably having a carbon number of 6 to 10 base.

Further, the heterocyclic group containing at least one selected from the group consisting of an oxygen atom and a sulfur atom is not contained in the nitrogen atom, and examples of the heterocyclic ring include a furan ring, a benzofuran ring, a thiophene ring, and a benzothiophene ring. A thienothiophene ring, a fluorinated furan ring, a thienofuran ring, and the like. The hydrocarbon group or the heterocyclic group of the above R ^d is preferably from 1 to 10 carbon atoms from the viewpoint of developability.

The Z-based system is preferably a hydrogen atom from the viewpoint of developability and luminance. On the other hand, the solvent solubility and compatibility can be improved by the Z system-(C=O)R ^d described above.

In the above general formula (1), R ^e is a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include those having 1 to 10 carbon atoms in the hydrocarbon group described in the above R ^c . In particular, from the viewpoint of enhancing sensitivity, the above R ^{e is} preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly excellent carbon. Alkyl groups of 1 to 4, preferably methyl groups.

The molecular weight of the oxime ester compound represented by the above formula (1) is not particularly limited, and is preferably 1,000 or less, and more preferably 800 or less from the viewpoint of reducing the content of the photoinitiator.

The oxime ester compound represented by the above general formula (1) is, for example, that R ^a and R ^b are each an alkyl group having 1 to 4 carbon atoms, R ^c is an alkyl group having 1 to 4 carbon atoms, and Z is a hydrogen atom or R. ^e is a compound having an alkyl group having 1 to 4 carbon atoms; R ^a and R ^b are each an alkyl group having 1 to 6 carbon atoms; and R ^c is a combination of a linear alkyl group and a cyclic alkyl group having 4 to 10 carbon atoms; a compound in which an alkyl group, Z is a hydrogen atom, and R ^e is an alkyl group having 1 to 4 carbon atoms; R ^a and R ^b are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^c is a carbon number of 1 to 4; The alkyl group, Z is -(C=O)R ^d , R ^d is an aryl group having 6 to 10 carbon atoms, and R ^e is a compound having an alkyl group having 1 to 4 carbon atoms, but is not limited thereto.

More preferably, the oxime ester compound represented by the above formula (1) is at least one selected from the group consisting of the following compounds (1-1) to (1-4): [Chemical 3]

The oxime ester compound represented by the above general formula (1) is, for example, referred to Japanese Patent Laid-Open Publication No. 2012-526185, and instead of diphenyl sulfide or a derivative thereof, a ruthenium or a derivative thereof is used instead, by using a material to be used. It can be synthesized by appropriately selecting a solvent, a reaction temperature, a reaction time, a purification method, and the like.

The coloring resin composition of the present invention preferably has two or more kinds of photoinitiators, from the viewpoint that the coloring layer which is improved in luminance can be formed and the sensitivity is good, and the line width can be easily adjusted at the time of pattern formation. An oxime ester compound of a carbazole skeleton. The oxime ester compound which does not have a carbazole skeleton is difficult to cause coloring because the reaction residue is hard to be colored, so that the decrease in the luminance of the colored layer can be suppressed. In addition, by appropriately selecting two or more kinds of oxime ester compounds containing the oxime ester compound represented by the above general formula (1) and having different sensitivities, the line width at the time of pattern formation can be adjusted while maintaining good sensitivity. When the colored resin composition of the present invention contains two or more kinds of oxime ester compounds having no carbazole skeleton, at least one or more kinds of the oxime ester compounds represented by the above formula (1) may be contained, and two types may be contained. The oxime ester compound represented by the above general formula (1) may be combined with other oxazole compounds containing the oxime ester compound represented by the above general formula (1) and the oxime ester compound different from the above general formula (1). The oxime ester compound of the skeleton.

Among them, from the viewpoint of not greatly reducing the luminance, developability, and sensitivity, and easily increasing the shape of the micropore, it is preferred to use the oxime ester compound represented by the above general formula (1) in combination with the diphenyl sulfide skeleton. An oxime ester compound.

As the oxime ester compound having a diphenyl sulfide skeleton, for example, an oxime ester compound represented by the following general formula (2) can be used: [Chemical Formula 4] General Formula (2) (In the general formula (2), R ^{c '} and R ^f each independently may contain at least one selected from the group consisting of a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-). a divalent linking group having 1 to 14 carbon atoms; Z ^{1 being} a hydrogen atom, a nitro group or -(C=O)R ^{d '} ; and the R ^{d '} system may also be selected from an oxygen atom and a sulfur atom. At least one type of hydrocarbon group or a heterocyclic group which does not contain a nitrogen atom but contains at least one selected from the group consisting of an oxygen atom and a sulfur atom.

R ^{c '} and R ^f of the above general formula (2) may further contain at least one divalent valence selected from a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-). The hydrocarbon group having 1 to 14 carbon atoms of the linking group may be, for example, R ^c of the above general formula (1), and may also contain a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond ( Among the hydrocarbon groups of at least one divalent linking group selected in -CO-), those having a carbon number of 1 to 14 are the same. It is also preferable that R ^{c ' of the} above general formula (2) is preferably a user of R ^{c of the} above general formula (1). The R ^{f of the} above general formula (2) is preferably an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of enhancing sensitivity. The base is a particularly preferred alkyl group having 1 to 4 carbon atoms.

The Z ¹ -based hydrogen atom, the nitro group or the -(C=O)R ^{d′ of the} above general formula (2); the R ^d′ system may further contain at least one hydrocarbon group selected from the group consisting of an oxygen atom and a sulfur atom, or However, selection of a nitrogen atom containing heterocyclic group is at least one selected from oxygen atom and sulfur atom; the R ^{d 'and} R lines can be exemplified as the above general formula (1) ^d of the same person. In the above Z ¹ , from the viewpoint of developability and luminance, a hydrogen atom or -(C=O)R ^{d ' is} preferable, and a hydrogen atom is more preferable from the viewpoint of luminance.

The molecular weight of the oxime ester compound represented by the above formula (2) is not particularly limited, and is preferably 1,000 or less, and more preferably 800 or less from the viewpoint of reducing the content of the photoinitiator.

The oxime ester compound represented by the above general formula (2) is, for example, R ^{c '} is a C 6-10 alkyl group in which a linear alkyl group and a cyclic alkyl group are combined; Z ¹ is a hydrogen atom, and R ^f is a compound having an alkyl group having 1 to 4 carbon atoms; R ^c' is a C 6-10 alkyl group in which a linear alkyl group and a cyclic alkyl group are combined, and Z ¹ is -(C=O)R ^{d '} , R ^{d '} is a compound having no nitrogen atom but a sulfur atom-containing heterocyclic group, and R ^f is a C 1-4 alkyl group, but is not limited thereto.

More preferably, the oxime ester compound represented by the above formula (2) is at least one selected from the group consisting of the following compounds (2-1) to (2-2).

[Chemical 5]

The oxime ester compound represented by the above general formula (2) can be synthesized, for example, by referring to JP-A-2012-526185.

In the photosensitive coloring resin composition for a color filter of the present invention, the photoinitiator may further be used in combination with other photoinitiators other than the above oxime ester compound. Further, the photoinitiator used in the colored resin composition of the present invention may further contain a chain transfer agent in addition to the photopolymerization initiator.

 <Other photoinitiators>  

Other photoinitiators include, for example, other oxime ester photoinitiators and α-amine ketones which are different from the oxime ester compound which covers the oxime ester compound represented by the above general formula (1) and which does not have a carbazole skeleton. Starting agent, biimidazole photoinitiator, oxygen sulfur A photoinitiator, a phosphine oxide-based photoinitiator, a hydrazine chain transfer agent, and the like.

In particular, from the viewpoint of improving the linearity when forming a fine line pattern, or improving the ability to form a thin line pattern such as a line width of a mask, and the viewpoint of enhancing the shape of a minute hole, the above general formula ( 1) The oxime ester compound shown is preferably further combined from an α-amine ketone photoinitiator, a diimidazole photoinitiator, and oxygen sulphur At least one selected from the group consisting of a photoinitiator, a phosphine oxide-based photoinitiator, and a quinone-based chain transfer agent. Among them, from the viewpoint of suppressing the chattering of the end portions of the micropores and suppressing the formation of fine pores with good dimensional accuracy, it is preferable to further use a bismuth phosphine oxide photoinitiator in combination. Since the pyridinium phosphine oxide photoinitiator has a higher thermal decomposition temperature than other initiators, it is less likely to cause side reactions due to heating during prebaking, and it is considered that chattering can be suppressed.

The term "elevation linearity" means that after the coloring composition is applied, the unevenness of the end portion of the colored layer formed in the developing step is small, and it is linear or slightly linear. In addition, "trembling" means that the straight line or the curved line at the end of the pattern is uneven, resulting in a deterioration in dimensional accuracy.

Further, from the viewpoint of enhancing the shape of the micropore and suppressing the tremor, it is preferable to use an α-amine ketone photoinitiator or a diimidazole photoinitiator in combination with the oxime ester compound represented by the above general formula (1). Oxygen and sulfur At least one selected from the group consisting of a photoinitiator, a phosphine oxide-based photoinitiator, and a quinone-based chain transfer agent, and an oxime ester compound having a diphenyl sulfide skeleton, and more preferably used in combination with an antioxidant .

Since the α-aminoketone-based photoinitiator has a property of hardening from the surface of the coating film, it is easy to suppress the deep curing property of the coating film. Therefore, when it is combined with the oxime ester compound represented by the above general formula (1), the coating is improved. It is preferred that the film has a tendency to be deep-hardenable.

The α-aminoketone-based photoinitiator may, for example, be 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (for example, IRGACURE 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone (for example, IRGACURE 369, manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( 4- Polinyl)phenyl]-1-butanone (IRGACURE 379EG, manufactured by BASF Corporation).

The α-aminoketone-based photoinitiator may be used alone or in combination of two or more. Among them, 2-methyl-1-(4-methylthiophenyl) is preferred from the viewpoint of enhancing the residual film ratio. )-2- Lolinylpropan-1-one and 2-benzyl-2-(dimethylamino)-1-(4- Phenylphenyl)-1-butanone; from the viewpoint of suppressing micropore tremor, 2-methyl-1-(4-methylthiophenyl)-2- is more preferred Lolinylpropan-1-one.

The diimidazole-based photoinitiator has a property of deepening the coating film in a deep portion, and is easy to suppress the surface hardenability of the coating film. When combined with the oxime ester compound represented by the above general formula (1), the surface of the coating film has a high tendency to be cured. In terms of opinion, it is preferred.

The diimidazole-based photoinitiator may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1. 2'-diimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4-dichlorobenzene -4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-di Imidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis (2, 4,6-Tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole.

The diimidazole-based photoinitiator may be used alone or in combination of two or more. From the viewpoint of improving the film curability, it is preferably used in combination with a lanthanide chain transfer agent.

Oxygen and sulfur The photoinitiator can be, for example, 2,4-isopropyloxysulfur 2,4-diethyloxysulfide 1-chloro-4-propoxyoxysulfide 2,4-dichlorooxosulfur Wait.

Oxygen and sulfur The photoinitiator may be used alone or in combination of two or more. Among them, from the viewpoint of enhancing the radical-generating transfer, it is preferred to use 2,4-isopropyloxysulfide. 2,4-diethyloxysulfide .

Although the bismuth phosphine oxide-based photoinitiator has a property of less yellowing due to heat, it is suitable for brightness enhancement, but generally, the sensitivity is low and sufficient hardenability cannot be obtained. However, when combined with the oxime ester compound represented by the above general formula (1), the overall film hardenability is improved, and when the micropores are formed, the tremor at the end of the pores can be suppressed, and the dimensional accuracy can be easily formed. Holes are preferred in this regard.

The phosphine oxide-based photoinitiator may, for example, be benzylidene-diphenylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, 2,3, 5,6-tetramethylbenzimidyl-diphenylphosphine oxide, 3,4-dimethylbenzimidyl-diphenylphosphine oxide, 2,4,6-trimethylbenzylidene- Phenylethoxylated phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4, 4-trimethyl-pentylphosphine oxide, bis(2,6-dimethylbenzylidene)-ethylphosphine oxide, and the like.

The bismuth phosphine oxide-based photoinitiator may be used alone or in combination of two or more. From the viewpoint of improving the film curability, it is preferred to use bis(2,4,6-trimethylbenzene). Mercapto)-phenylphosphine oxide.

The oxime chain transfer agent has a property of accelerating a reaction from a radical having a slow reaction, and accelerating the reaction. In particular, from the viewpoint of increasing the reaction rate, it is preferred to use a diimidazole photoinitiator in combination.

The lanthanide chain transfer agent may, for example, be 2-mercaptobenzothiazole or 2-mercaptobenzoene. Oxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, 3 - ethyl mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1 , 3,5-three -2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropane) Acid ester), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

The lanthanide chain transfer agent may be used singly or in combination of two or more kinds, and from the viewpoint of increasing the reaction rate, 2-mercaptobenzothiazole is preferably used.

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, and is used for a color filter. The total amount of the solid content of the photosensitive colored resin composition is preferably 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less. When the content is at least the above lower limit value, the photocuring is sufficiently promoted, and the exposed portion is prevented from being eluted during development; on the other hand, when the content is at most the above upper limit, the yellowing property of the obtained colored layer can be suppressed from increasing. Causes the brightness to decrease.

In addition, the "solid content" means all than the solvent, and also includes a liquid polyfunctional monomer.

In the photosensitive colored resin composition for a color filter of the present invention, the content of the oxime ester compound represented by the above general formula (1) is used, and the total amount of the solid content of the photosensitive colored resin composition for a color filter is used. It is preferably 0.1% by mass or more and 8.0% by mass or less, more preferably 0.5% by mass or more and 6.0% by mass or less. When the content is at least the above lower limit value, photocuring is sufficiently promoted to suppress elution of the exposed portion during development; on the other hand, when the content is at most the above upper limit, the yellowing property of the obtained colored layer can be suppressed from increasing. Causes the brightness to decrease.

In addition, when the photoinitiator contains two or more oxime ester compounds which do not have a carbazole skeleton, the photosensitive coloring resin composition for color filters of the present invention contains the oxime ester compound represented by the above general formula (1). The total content of the oxime ester compound having two or more kinds of carbazole skeletons, and the photosensitive colored resin composition for color filters are solid-formed from the viewpoint of sufficiently exhibiting the effect of using the photoinitiator together. The total amount of the parts is preferably 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less.

Further, when the photoinitiator used in the present invention is the oxime ester compound represented by the above general formula (1), when the above oxime ester compound having a diphenyl sulfide skeleton is combined, the above-mentioned diphenyl sulfide skeleton is used. The content of the oxime ester compound is sufficient to exhibit the photosensitivity with respect to the color filter from the viewpoint of the combined effect of the oxime ester compound represented by the above general formula (1) and the oxime ester compound having the diphenyl sulfide skeleton. The total amount of the solid content of the colored resin composition is preferably 0.1% by mass or more and 4.0% by mass or less, more preferably 0.3% by mass or more and 3.0% by mass or less.

When the photoinitiator used in the present invention is an oxime ester compound represented by the above general formula (1), the oxime ester compound represented by the above general formula (1) is used in combination with the above oxime ester compound having a diphenyl sulfide skeleton. And the ratio of the oxime ester compound having a diphenyl sulfide skeleton to the above-mentioned diphenyl sulfide skeleton with respect to 100 parts by mass of the oxime ester compound represented by the above general formula (1) from the viewpoint of luminance and sensitivity The oxime ester compound is preferably 10 parts by mass or more and 150 parts by mass or less, more preferably 15 parts by mass or more and 120 parts by mass or less. The oxime ester compound having a diphenyl sulfide skeleton is preferably 10 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the oxime ester compound represented by the above general formula (1), from the viewpoint of the formation of the micropores. More preferably, it is 15 mass parts or more and 50 mass parts or less.

Further, in the photosensitive coloring resin composition for a color filter of the present invention, when the photoinitiator further contains a photoinitiator other than the above, the oxime ester compound represented by the above formula (1) and the above The total content of the oxime ester compound having a diphenyl sulfide skeleton is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, based on 100 parts by mass of the total of the photoinitiator used in the present invention. More than 50 parts by mass.

On the other hand, the total content of the oxime ester compound represented by the above general formula (1) and the oxime ester compound having the diphenyl sulfide skeleton is from the viewpoint of sufficiently exerting the effect of the use of the other photoinitiator other than the above. In the total of 100 parts by mass of the photoinitiator used in the present invention, it is preferably 95 parts by mass or less, more preferably 85 parts by mass or less.

When the photoinitiator used in the present invention further contains an α-amine ketone photoinitiator, a diimidazole photoinitiator, and oxygen sulfur When at least one selected from the group consisting of a photoinitiator, a phosphine oxide-based photoinitiator, and a quinone-based chain transfer agent is used, from the viewpoint of sufficiently exerting the effect together with the photoinitiator, In the total amount of the solid content of the photosensitive colored resin composition for a color filter, the total content of these is preferably 0.1% by mass or more and 4.0% by mass or less, more preferably 0.5% by mass or more and 2.0% by mass or less. .

 [color material]  

In the present invention, the color material is not particularly limited as long as it can form a desired color when the colored layer of the color filter is formed, and two or more kinds of various organic pigments, inorganic pigments, and the like can be used singly or in combination. Dispersible dyes and dyes. Among them, organic pigments are preferred because of their high color developability and high heat resistance. The organic pigment is a compound classified as a pigment in the pigment index (C.I.; The Society of Dyers and Colourists, Inc.), and specifically, for example, a pigment index (C.I.) is given as follows.

In the case where the pigment index name is described below, when only the number of the listed pigment index names is different, only the number may be listed.

CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155 , 156, 166, 168, 175, 185; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI pigment purple 1, 19, 23, 29, 32, 36, 38; CI pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49: 1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190 193,194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265; CI Pigment Blue 15, 15:3, 15:4 , 15:6, 60; CI pigment green 7, 36, 58, 59; CI pigment brown 23, 25; CI pigment black 1, 7.

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

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

The above dispersible dye may, for example, be a dispersible dye which is insoluble in a solvent by imparting various substituents to the dye; a dispersible dye by using a solvent having a low solubility in combination; and being soluble in a solvent The dye forms a salt with the counterion and does not dissolve (paste) the lake color material. By using such a dispersible dye and a dispersing agent, the dispersibility and dispersion stability of the dye can be improved.

Further, when the amount of the dye dissolved in 10 g of the solvent (or the mixed solvent) is 100 mg or less, it can be judged that the dye can be dispersed in the solvent (or mixed solvent).

The above dyes can be appropriately selected from conventionally known dyes. Such a dye may, for example, be an azo dye, a metal salt azo dye, an anthraquinone dye, a triphenylmethane dye, a dibenzopyran dye, an anthocyanin dye, a naphthoquinone dye, a quinone imine dye, or the like. Methyl dyes, phthalocyanine dyes, and the like. Specifically, for example, CI Solvent Yellow 4, 14, 15, 24, 82, 88, 94, 98, 162, 179; CI Solvent Red 45, 49; CI Solvent Orange 2, 7, 11, 15, 26, 56 CI solvent blue 35, 37, 59, 67; CI acid red 50, 52, 289; CI acid purple 9, 30; CI acid blue 19 and so on.

When a blue colored layer is formed, it is particularly preferably at least one of a triarylmethane dye, a dibenzopyran dye, and an anthocyanin dye from the viewpoint of high luminance, and has high heat resistance. From the viewpoint of the above, at least one selected from the group consisting of a triarylmethane dye and a dibenzopyran dye is preferred.

In the present invention, from the viewpoint of enhancing the luminance of the color filter, it is preferred to contain a lake color material having a triarylmethane-based dye, and more preferably a triarylmethane-based basic dye, and a polyoxometallate. Salt anion.

In the present invention, the coloring lake material is preferably a color material as shown in the following general formula (i) from the viewpoint of excellent heat resistance and light resistance and high color brightness of the color filter to form a molecular association. The state is preferred from the viewpoint of more excellent heat resistance.

[Chemical 6] General formula (i)

(In the general formula (i), A represents an a-valent organic group in which a carbon atom directly bonded to N does not have a π bond, and the organic group represents a saturated aliphatic hydrocarbon group at least at a terminal directly bonded to N. The aliphatic hydrocarbon group or the aromatic group having the aliphatic hydrocarbon group may contain O, S, and N in the carbon chain. The B ^c- system represents a c-valent polyoxometalate anion. R ⁱ to R ^v represent each An alkyl group which may independently be a hydrogen atom, may have a substituent, or an aryl group which may have a substituent, may also be bonded to a ring structure by R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v . Ar ¹ means a divalent aromatic group having a substituent. The complex numbers R ⁱ to R ^v and Ar ¹ may be the same or different.

a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. The e-system is 0 or 1, and when e is 0, there is no bond. The plural e-systems may be the same or different. )

The cation portion of the color material represented by the above general formula (i) may be the same as the cation portion of the color material represented by the general formula (i) described in International Publication No. 2012/144521.

The carbon atom directly bonded to the A system and the N (nitrogen atom) in the above general formula (i) has no a-valent organic group having a π bond, and the organic group means having a saturated fat at least at the terminal directly bonded to N. The aliphatic hydrocarbon group of the hydrocarbon group or the aromatic group having the aliphatic hydrocarbon group may further contain O (oxygen atom), S (sulfur atom), or N (nitrogen atom) in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics of the cationic color-developing portion such as color tone and transmittance are not affected by the linker A and other color-developing portions, and can be maintained. The same color of the monomer.

In A, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N is lifted before the terminal carbon atom directly bonded to N has a π bond, and may be linear, branched or cyclic. The carbon atoms other than the terminal may have an unsaturated bond, may have a substituent, and may also contain O, S, and N in the carbon chain. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, a guanamine group or the like may be contained, and a hydrogen atom may be further substituted with a halogen atom or the like.

Further, in the above, the aromatic group having an aliphatic hydrocarbon group may, for example, be a monocyclic or polycyclic aromatic group containing an aliphatic hydrocarbon group which is a saturated aliphatic hydrocarbon group at least at a terminal directly bonded to N. It may have a substituent or a heterocyclic ring containing O, S, and N.

Among them, from the viewpoint of skeleton fastness, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group.

From the viewpoint of skeleton fastness, the cyclic aliphatic hydrocarbon group is preferably a bridged aliphatic hydrocarbon group. The term "bridged alicyclic hydrocarbon group" refers to a polycyclic aliphatic hydrocarbon group having a polycyclic structure and having a bridge structure in an aliphatic ring, for example, Alkane, bicyclo[2,2,2]octane, dicyclopentadiene, adamantane, and the like. Preferred to have a bridged alicyclic hydrocarbon group alkyl. Further, the aromatic group may, for example, contain a group of a benzene ring or a naphthalene ring, and among them, a group containing a benzene ring is preferred.

From the viewpoint of easiness of obtaining raw materials, A is preferably two or more and four or less, more preferably two or more and three or less, and particularly preferably two. For example, in the case of the A-based divalent organic group, for example, a linear, branched or cyclic alkylene group having 1 or more and 20 or less carbon atoms; and a carbon number of 1 or more such as two exophthalene groups; An alkyl group-substituted aromatic group of 20 or less.

The alkyl group of R ⁱ to R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 or more carbon atoms and 20 or less carbon atoms is particularly preferably a linear or branched alkyl group having 1 or more carbon atoms and 8 or less carbon atoms, and is more convenient from the viewpoint of ease of production and raw material scheduling. A linear or branched alkyl group having 1 or more carbon atoms and 5 or less carbon atoms is preferred. Among them, the alkyl group of R ⁱ to R ^v is particularly preferably an ethyl group or a methyl group. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group, and the substituted alkyl group may, for example, be a benzyl group.

The aryl group of R ⁱ to R ^v is not particularly limited. For example, phenyl, naphthyl and the like. The substituent which the aryl group may have may, for example, be an alkyl group or a halogen atom.

The phrase "bonding R ⁱⁱ to R ⁱⁱⁱ and R ^iv to R ^v to form a ring structure" means that R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v form a ring structure via a nitrogen atom. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring and a piperidine ring. A porphyrin ring or the like.

Among them, from the viewpoint of chemical stability, R ⁱ to R ^{v are} preferably each independently a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v phase bonding forms a pyrrolidine ring, a piperidine ring, A porphyrin ring.

R ⁱ to R ^v may each independently form the above-described structure, but from the viewpoint of color purity, R ^{i is} preferably a hydrogen atom, and from the viewpoint of ease of manufacture and raw material scheduling, R ⁱⁱ ~ is preferable. R ^{v is} all the same.

The divalent aromatic group of Ar ¹ is not particularly limited. The aromatic group may be a heterocyclic group in addition to the aromatic hydrocarbon group composed of a carbocyclic ring. The aromatic hydrocarbon-based aromatic hydrocarbon-based benzene ring may, for example, be a condensed polycyclic aromatic hydrocarbon such as a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring or a phenanthrene ring; Chain polycyclic hydrocarbons such as triphenyl, diphenylmethane, triphenylmethane, and anthracene. In the chain polycyclic hydrocarbon, O, S, and N may be contained in the chain skeleton such as diphenyl ether. On the other hand, the heterocyclic ring heterocyclic ring may, for example, be furan, thiophene or pyrrole. 5-membered heterocyclic ring such as azole, thiazole, imidazole or pyrazole; pyran, pipenone, pyridine, piperone, hydrazine Pyrimidine, pyridyl Equal six-membered heterocyclic ring; benzofuran, thiazide, anthracene, oxazole, coumarin, benzopiperone, quinoline, isoquinoline, acridine, anthracene Quinazoline, quinolin A condensed polycyclic heterocyclic ring such as a phenyl group. These aromatic groups may have a substituent.

The substituent which the aromatic group may have is, for example, an alkyl group having 1 or more and 5 or less carbon atoms, a halogen atom or the like.

Ar ^{1 is} preferably an aromatic group having 6 or more and 20 or less carbon atoms, more preferably an aromatic group composed of a condensed polycyclic carbocyclic ring having 10 or more and 14 or less carbon atoms. Among them, from the viewpoints of simple structure and low raw materials, it is more preferred to extend a phenyl group and a naphthyl group.

The complex numbers R ⁱ to R ^v and Ar ^{1 in} one molecule may be the same or different. When the plural numbers R ⁱ to R ^v and Ar ¹ are the same, since the color-developing portions have the same color, they can exhibit the same color as the monomers of the color-developing portion, and from the viewpoint of color purity, good. On the other hand, when at least one of R ⁱ to R ^v and Ar ¹ is a different substituent, the color mixed by a plurality of monomers can be reproduced and adjusted to a desired color.

The anion (B ^c- ) of the color material represented by the above formula (i) is a divalent or higher polyoxometallate anion.

Among them, the polyoxometallate anion preferably contains at least one polyoxometalate anion of tungsten (W) and molybdenum (Mo) from the viewpoint of high luminance, heat resistance, and light resistance. From the viewpoint of heat resistance, a polyoxometallate anion containing at least tungsten and containing molybdenum is more preferable.

In the polyoxometalate anion containing at least tungsten (W), the content ratio of tungsten to molybdenum is not particularly limited, and in particular, from the viewpoint of excellent heat resistance, the molar ratio of tungsten to molybdenum is preferably 100:0~ Within the range of 85:15, better in the range of 100:0~90:10.

The polyoxometalate anion (B ^c- ) may be used alone or in combination of two or more kinds. When two or more kinds are used in combination, the polyoxometallate anion is tungsten in the whole. The molar ratio to molybdenum is preferably within the above range.

The color material represented by the above general formula (i) may form a double salt further containing other cations or anions insofar as it does not impair the effects of the present invention. Specific examples of such a cation include, in addition to other basic dyes, an organic compound containing a functional group capable of forming a salt with an anion such as an amine group, a pyridyl group or an imidazolyl group; sodium ion, potassium ion, magnesium Metal ions such as ions, calcium ions, copper ions, and iron ions. Further, specific examples of the anion include, in addition to the acid dye, halide ions such as fluoride ions, chloride ions, and bromide ions; and anions of inorganic acids. Examples of the anion of the inorganic acid include an anion of an oxo acid such as a phosphate ion, a sulfate ion, a chromanic ion, a tungstic acid ion (WO ₄ ^2- ), or a molybdate ion (MoO ₄ ^2- ).

Further, the color material represented by the general formula (i) is prepared, for example, by referring to International Publication No. 2012/144520.

Further, in the case of forming a green colored layer, it is preferable to use a green color material of a yellow color material in C.I. Pigment Green 59 (PG59) and C.I. Pigment Green 58 (PG58) which are zinc phthalocyanine pigments.

A yellow color material which can be used in combination with a zinc phthalocyanine pigment such as PG59 or PG58 is particularly preferably a derivative pigment of C.I. Pigment Yellow 150. The derivative pigment of CI Pigment Yellow 150 may specifically be a single, two or three azo compound according to one of the following general formula (ii) or its tautomeric structure having at least one guest compound main body. And tetraanions, and metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb (particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La) Metal body. From the viewpoint of enhancing the luminance, it is preferred to use such a derivative pigment of C.I. Pigment Yellow 150.

(In the above general formula (ii), R ³¹ is each independently OH, NH ₂ , NH-CN, a halogenated amine group, an alkylamino group, or an arylamine group; and the R ³² groups are each independently -OH or - NH ₂ )

Among them, the yellow color material preferably contains, from the viewpoint of enhancing the luminance and improving the contrast, the azo compound represented by the above general formula (ii) and the azo compound of the tautomeric structure thereof. At least one anion selected from the group consisting of tri- and tetra-anions, and at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn ion.

By containing two or more kinds of metal ions, the crystal growth of the color material can be suppressed, and the micronization can be suppressed. Further, since it is used in combination with a dispersant described later, it is micronized in the dispersion of the color material, and it is presumed that a contrast can be formed. The color layer.

The mercapto group of the deuterated amino group in the general formula (ii) may, for example, be an alkylcarbonyl group, a phenylcarbonyl group, an alkanesulfonyl group or a benzenesulfonyl group; or an amine group which may be substituted by an alkyl group, a phenyl group or a naphthyl group. Anthracenyl; an aminesulfonyl group which may be substituted by an alkyl group, a phenyl group or a naphthyl group; a guanyl group which may be substituted by an alkyl group, a phenyl group or a naphthyl group. The above alkyl group is preferably a carbon number of 1 to 6. Further, the above alkyl group may be substituted with, for example, a halogen such as F, Cl or Br; or -OH, -CN, -NH ₂ and/or an alkoxy group having 1 to 6 carbon atoms. Further, the phenyl group and the naphthyl group may be, for example, a halogen such as F, Cl or Br; -OH, -CN, -NH ₂ , -NO ₂ , an alkyl group having 1 to 6 carbon atoms, and/or a carbon number of 1~. Substituted by an alkoxy group of 6.

The alkyl group of the alkylamino group in the general formula (ii) is preferably a carbon number of 1 to 6. The above alkyl group may be substituted with, for example, a halogen such as F, Cl or Br; -OH, -CN, -NH ₂ and/or an alkoxy group having 1 to 6 carbon atoms.

The aryl group of the arylamine group in the general formula (ii) may, for example, be a phenyl group or a naphthyl group, and the aryl group may be, for example, a halogen such as F, Cl or Br; -OH, a carbon number of 1 to 6; The alkyl group, the alkoxy group having 1 to 6 carbon atoms, -NH ₂ , -NO ₂ and -CN are substituted.

The azo compound represented by the above general formula (ii) and the azo compound thereof having a tautomeric structure, from the viewpoint of hue, R ^{31 is} preferably each independently -OH, -NH ₂ , -NH-CN, or alkyl group, two R ³¹ may each be the same or different.

In the above general formula (ii), from the viewpoint of hue, it is preferable that both R ³¹ are both -OH, both are -NH-CN, or one is -OH and the other is In the case of -NH-CN, both of them are -OH.

Further, in the azo compound represented by the above formula (ii) and the azo compound having a tautomeric structure, R ^{32 is more} preferably both -OH from the viewpoint of hue.

When at least two metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn are contained, the at least two metals preferably contain at least one metal A metal which is a divalent or trivalent cation, more preferably contains at least one selected from the group consisting of Ni, Cu, and Zn, and particularly preferably contains at least Ni.

Further, it is preferable to contain Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn, and more preferably Ni and Zn, Cu. At least one metal selected from the group consisting of Al and Fe. Among them, the at least two metals are preferably Ni and Zn, or Ni and Cu, and more preferably Ni and Zn from the viewpoint of affinity with the zinc phthalocyanine pigment.

When ions of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn are contained, the content ratio of at least two metals may be appropriately adjusted. .

Wherein, the content ratio of Ni and at least one metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn is preferably Ni: the other at least one of the above The metal is 97:3~10:90, and the molar ratio is 90:10~10:90.

Among them, Ni and Zn are preferably contained in a molar ratio of Ni:Zn of 90:10 to 10:90, and more preferably by a molar ratio of 70:30 to 10:90. Among them, when combined with a zinc phthalocyanine pigment, the ratio of Ni to Zn preferably contains Zn more than Ni, more preferably Ni and Zn, from the viewpoint of improving the coloring power and easily suppressing the development residue in the micropores. Ni: Zn is contained in a molar ratio of 40:60 to 10:90.

Alternatively, Ni and Cu are preferably contained in a molar ratio of Ni:Cu of 97:3 to 10:90, and more preferably by a molar ratio of 96:4 to 20:80.

When an ion of at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn is contained, the derivative pigment of CI Pigment Yellow 150 may also contain A metal ion different from the ion of the above specific metal. For example, at least one metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La may be contained.

The pigment of CI Pigment Yellow 150 contains at least two types of metal ions, and may include, for example, a case where at least two kinds of metal ions are contained in the common crystal lattice, and each of the other crystal lattices A case where a crystal of one metal ion is agglomerated. Among them, from the viewpoint of further improvement of contrast, it is preferred that at least two kinds of metal ions are contained in the common crystal lattice. In addition, in the case of a state in which at least two metal ions are contained in a common crystal lattice, or a state in which crystallization is carried out by containing one metal ion in each of the other crystal lattices, for example, refer to Japanese Patent Laid-Open Publication No. 2014 The -12838 bulletin can be appropriately judged by using the X-ray diffraction method.

The average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as the desired coloring can be performed when forming the colored layer of the color filter, depending on the type of color material used. The difference 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 within the above range, a display device using the color filter produced by using the color material dispersion of the present invention can be provided with high contrast and high quality.

The color material used in the present invention can be produced by a known method such as a recrystallization method or a solute solvent polishing method. Further, the commercially available color material may be subjected to miniaturization treatment before being used.

The total content of the color material is preferably from 3% by mass to 65% by mass, more preferably from 4% by mass to 60% by mass based on the total amount of the solid content of the photosensitive colored resin composition for the color filter. Blending. When the color filter is coated with a photosensitive colored resin composition to have a predetermined film thickness (usually 1.0 μm to 5.0 μm), the color layer can have a sufficient color density. In addition, when it is at most the above upper limit value, it is excellent in storage stability, and a coloring layer having sufficient hardness and adhesion to a substrate can be obtained. In particular, when a coloring layer having a high color material concentration is formed, the total content of the color materials is preferably 15% by mass to 65% by mass based on the total amount of the solid content of the photosensitive colored resin composition for the color filter. More preferably, the ratio is 255% by mass to 60% by mass.

 [alkali soluble resin]  

The alkali-soluble resin of the present invention has an acidic group and can be appropriately selected from those which have a binder resin action and are soluble in the alkali developer used for pattern formation.

In the present invention, the "alkali-soluble resin" can be used as an index of an acid value of 40 mgKOH/g or more.

The preferred alkali-soluble resin of the present invention is a resin having an acidic group (usually a carboxyl group), and specific examples thereof include an acrylic resin having a carboxyl group and an acrylic resin such as a styrene-acrylic copolymer having a carboxyl group; A carboxyl group-containing epoxy (meth) acrylate resin or the like. Among these, a particularly preferred side chain has a carboxyl group, and the side chain further has a photopolymerizable functional group such as an ethylenically unsaturated group. The reason is that the film strength of the formed cured film can be improved by containing a photopolymerizable functional group. Further, two or more kinds of the acrylic resin and the epoxy acrylate resin such as the acryl-based copolymer and the styrene-acrylic copolymer may be used in combination.

Examples of the acrylic resin such as an acryl-based copolymer having a carboxyl group-constituting unit and a styrene-acrylic copolymer having a carboxyl group include, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, other monomers copolymerizable. A (co)polymer obtained by (co)polymerization by a known method.

The carboxyl group-containing ethylenically unsaturated single system may, for example, be (meth)acrylic acid, vinyl benzoate, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid. , crotonic acid, cinnamic acid, acrylic acid dimer, and the like. Further, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a cyclic dehydrated product such as maleic anhydride, decanoic anhydride or cyclohexane dicarboxylic anhydride may be used. Addition reactant; and ω-carboxy-polycaprolactone mono(meth)acrylate and the like. Further, as the precursor of the carboxyl group, a dehydrated monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used. Among them, (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

The alkali-soluble resin is more preferably a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. It is known that the alkali-soluble resin has a hydrocarbon ring which is a bulky group, and the solvent resistance of the obtained colored layer can be suppressed, and in particular, the swelling of the colored layer can be suppressed. Although the related effects are not clear, it is presumed that the molecular action in the colored layer is suppressed by the inclusion of a large hydrocarbon ring in the colored layer, and as a result, the coating film strength is improved, and swelling due to the solvent is suppressed.

Examples of such a hydrocarbon ring system include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination thereof, and the hydrocarbon ring may have a carbonyl group, a carboxyl group, an oxycarbonyl group, or the like. A substituent such as a guanamine group. Among them, when an aliphatic ring is contained, heat resistance and adhesion of the colored layer can be improved, and the luminance of the obtained colored layer can be improved.

Specific examples of the hydrocarbon ring include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and descending. An aliphatic hydrocarbon ring such as alkane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane) or adamantane; an aromatic ring such as benzene, naphthalene, anthracene, phenanthrene or anthracene; biphenyl, hydrazine A chain polycyclic ring such as benzene, diphenylmethane, triphenylmethane or hydrazine; a cardo structure represented by the following chemical formula (A).

[Chemical Formula 8] Chemical Formula (A)

Further, the alkali-soluble resin preferably has a maleimide structure represented by the following general formula (B).

(In the general formula (B), the R ^{M group} may also be substituted with a hydrocarbon ring.)

When the alkali-soluble resin has the maleimide structure represented by the above general formula (B), since the hydrocarbon ring has a nitrogen atom, it is alkaline-dispersed with a polymer having a structural unit represented by the general formula (I) described later. The compatibility of the agent is very good, and the development residue suppressing effect is enhanced.

Specific examples of the hydrocarbon ring which may be substituted with R ^M of the above general formula (B) are exemplified by the above specific examples of the hydrocarbon ring.

When the hydrocarbon ring contains an aliphatic ring, it is preferred from the viewpoint of improving heat resistance and adhesion of the colored layer and improving the brightness of the obtained colored layer.

In addition, when the suspension structure represented by the above chemical formula (A) is contained, it is preferable from the viewpoint of improving the hardenability of the colored layer and improving the solvent resistance (NMP swelling inhibition).

The alkali-soluble resin used in the present invention is preferably a carboxyl group-containing resin from the viewpoint of easily adjusting the amount of each constituent unit and increasing the amount of the constituent unit having the hydrocarbon ring, and easily improving the function of the constituent unit. An acrylic copolymer having a hydrocarbon ring-constituting unit other than the constituent unit.

The carboxyl group-constituting unit and the above hydrocarbon-containing acryl-based copolymer can be produced by using the hydrocarbon-containing ethylenically unsaturated monomer of the above-mentioned "other monomer capable of copolymerization".

The hydrocarbon unsaturated monomer having a hydrocarbon ring used in combination with the oxime ester compound represented by the above general formula (1) may, for example, be cyclohexyl (meth)acrylate or dicyclopentanyl (meth)acrylate. Adamantyl (meth)acrylate, (meth)acrylic acid The ester, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, etc., can maintain the effect of the cross-sectional shape of the colored layer after development even after heat treatment. Preferred are cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, styrene, more preferably styrene.

Further, from the viewpoint of the effect of suppressing the development residue, the above-mentioned ethylenically unsaturated monomer having a hydrocarbon ring is preferably a monomer having a structure of maleimide and styrene, more preferably benzene. Ethylene.

The alkali-soluble resin used in the present invention is preferably a side chain having an ethylenic double bond. When the ethylenic double bond is present, in the resin composition hardening step in the production of the color filter, the alkali-soluble resin and the alkali-soluble resin and the photopolymerizable compound may form a cross-linking bond. By using in combination with the oxime ester compound of the above general formula (1) used in the present invention, the film strength of the cured film can be further enhanced, the development resistance can be improved, the heat shrinkage of the cured film can be suppressed, and the adhesion to the substrate can be excellent.

The method of introducing an ethylenic double bond into the alkali-soluble resin can be appropriately selected from conventionally known methods. For example, a compound having an epoxy group and an ethylenic double bond (for example, glycidyl (meth)acrylate) is added to a carboxyl group of an alkali-soluble resin, and an ethylenic double is introduced in the side chain. When a constituent unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond in a component and a method of introducing an ethylenic double bond into a side chain are added.

The alkali-soluble resin of the present invention may further contain other constituent units such as methyl (meth)acrylate, ethyl (meth)acrylate, and the like, and constituent units having an ester group. The constituent unit having an ester group not only has the function of suppressing the alkali-soluble component of the photosensitive colored resin composition for a color filter, but also has a function of improving the solvent solubility (and solvent resolubility) component.

The alkali-soluble resin of the present invention preferably has an acrylic resin such as a carboxyl group-containing constituent unit, an acrylic copolymer having a hydrocarbon ring-containing constituent unit, and a styrene-acrylic copolymer, and more preferably a carboxyl group-containing constituent unit. An acrylic resin having a structural unit of a hydrocarbon ring and an acrylic copolymer having a structural unit of an ethylenic double bond, and an acrylic resin such as a styrene-acrylic copolymer.

The alkali-soluble resin can be an alkali-soluble resin having desired properties by appropriately adjusting the loading amount of each constituent unit.

The loading amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, and more preferably 10% by mass or more based on the total amount of the monomers, from the viewpoint of obtaining a good pattern. On the other hand, the loading amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, more preferably 40, from the viewpoint of suppressing film roughness on the surface of the pattern after development. Below mass%.

When the proportion of the carboxyl group-containing ethylenically unsaturated monomer is at least the above lower limit value, the solubility of the obtained coating film to the alkali developing solution is sufficient, and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is at the above upper limit When the value is below the value, when the development is performed by the alkali developing solution, the formed pattern tends to be detached from the substrate or the surface film of the pattern tends to be rough.

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

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably in the range of 3,000 to 20,000. If it is less than 1,000, the function of the binder after hardening may be remarkably lowered, and if it exceeds 50,000, it may be difficult to form a pattern when developing with an alkali developer.

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

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

The epoxy compound and the unsaturated group containing a monocarboxylic acid and an acid anhydride can be appropriately selected from known ones. The epoxy (meth) acrylate resin having a carboxyl group may be used alone or in combination of two or more.

The alkali-soluble resin is preferably one having an acid value of 50 mgKOH/g or more from the viewpoint of developability (solubility) of the aqueous alkali solution used for the developer. The alkali-soluble resin is preferably an acid value of 70 mgKOH/g or more and 300 mgKOH/g or less, more preferably 70 mgKOH/or from the viewpoint of developability (solubility) of the aqueous alkali solution used for the developer and adhesion to the substrate. g or more and 280 mgKOH/g or less.

Further, in the present invention, the acid value can be measured in accordance with JIS K 0070.

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, an ethylenically unsaturated bond equivalent can be obtained by combining the above-described oxime ester compound represented by the general formula (1) used in the present invention to obtain a film strength of the cured film. From the viewpoint of improving the development resistance and the effect of excellent adhesion to the substrate, it is preferably in the range of 100 to 2,000, more preferably in the range of 140 to 1,500. When the ethylenic unsaturated bond equivalent is 2,000 or less, the development resistance and the adhesion are excellent. In addition, when the ratio is 100 or more, the ratio of the other constituent units such as the constituent unit having a carboxyl group and the constituent unit having a hydrocarbon ring is relatively increased, so that the developability and heat resistance are excellent. The oxime ester compound represented by the above general formula (1) used in the present invention is preferably used in the above-mentioned contents and combinations.

Here, the "ethylenically unsaturated bond equivalent" means the weight average molecular weight of the average ethylenically unsaturated bond 1 mol in the above alkali-soluble resin, as shown by the following formula (1): Formula (1) Ethylene Unsaturated bond equivalent (g/mol)=W(g)/M(mol)

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

The ethylenically unsaturated bond equivalent is calculated, for example, by measuring the number of ethylenic double bonds contained in an average of 1 g of the alkali-soluble resin according to the iodine value test method described in JIS K 0070:1992.

The alkali-soluble resin used for the coloring resin composition for a color filter may be used singly or in combination of two or more kinds, and the content is not particularly limited, and the photosensitivity for color filters is used. The total amount of the solid content of the colored resin composition is preferably from 5% by mass to 60% by mass, more preferably from 10% by mass to 40% by mass. When the content of the alkali-soluble resin is at least the above lower limit value, sufficient alkali developability can be obtained, and if the alkali-soluble resin content is at most the above upper limit value, film roughness and pattern defects can be suppressed during development.

 [Photopolymerizable compound]  

The photopolymerizable compound used for the photosensitive coloring resin composition for a color filter is prepared before being polymerized by the photoinitiator, and the rest is not particularly limited, and it is usually preferred to use two or more ethylene. The compound of the unsaturated double bond is particularly preferably a polyfunctional (meth) acrylate having two or more acrylonitrile groups or methacryl groups.

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

These polyfunctional (meth)acrylates may be used alone or in combination of two or more. Further, when the photosensitive coloring resin composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional (meth) acrylate preferably has a 3 (trifunctional) or higher polymerizable double bond. Preferred are poly(meth)acrylates of a trivalent or higher polyhydric alcohol, and such dicarboxylic acid modified materials, and specific examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol. (meth) acrylate, pentaerythritol tri(meth) acrylate succinic acid modification, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, A succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like.

The content of the photopolymerizable compound used in the photosensitive coloring resin composition for a color filter is not particularly limited, and the photopolymerizable property is the total solid content of the photosensitive colored resin composition for a color filter. The compound is preferably in the range of 5% by mass to 60% by mass, more preferably 10% by mass to 40% by mass. When the content of the photopolymerizable compound is at least the above-mentioned lower limit value, the photocuring is sufficiently performed, and the exposed portion is prevented from being eluted during development. When the content of the photopolymerizable compound is at most the above upper limit, the alkali developability is sufficient.

In the photosensitive coloring resin composition for a color filter, the content ratio of the photopolymerizable compound to the photoinitiator is used, and from the viewpoint of excellent curability and residual film ratio, and electrical reliability is improved. In view of the above, the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, based on 100 parts by mass of the photopolymerizable compound. More preferably, it is 30 mass parts or less.

 [solvent]  

The solvent to be used in the present invention is not affected by the reaction with each component in the photosensitive colored resin composition for a color filter, but it is not particularly limited as long as it can dissolve or disperse the organic solvent. The solvent may be used singly or in combination of two or more.

Specific examples of the solvent include alcohol solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxylated alcohol; methoxyethoxyethanol and ethoxyethoxyethanol; Carbitol solvent; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, hydroxyl Ethyl propionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate, etc.; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, acetic acid-3-methoxy-3-methyl-1-butyl ester, acetic acid a glycol ether acetate solvent such as -3-methoxybutyl ester or ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate a carbitol acetate solvent such as ester (BCA); a diacetate such as propylene glycol diacetate or 1,3-butylene glycol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Dimethyl ether, diethylene glycol a glycol ether solvent such as methyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether or dipropylene glycol dimethyl ether; N,N-dimethylformamide, N,N-di An aprotic guanamine solvent such as methyl acetamide or N-methylpyrrolidone; a lactone solvent such as γ-butyrolactone; a cyclic ether solvent such as tetrahydrofuran; benzene, toluene, xylene, naphthalene, etc. A saturated hydrocarbon solvent; a saturated hydrocarbon solvent such as N-heptane, N-hexane or N-octane; or an organic solvent such as an aromatic hydrocarbon such as toluene or xylene. Among these solvents, a glycol ether acetate solvent, a carbitol acetate solvent, a glycol ether solvent, or an ester solvent is preferably used from the viewpoint of solubility of other components. In particular, the solvent used in the present invention is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or butyl carbitol acetate (BCA) from the viewpoints of solubility of other components and coating suitability. One or more selected from the group consisting of 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate.

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

 [Dispersant]  

In the photosensitive colored resin composition for a color filter of the present invention, the color material is preferably used after being dispersed in a solvent using a dispersing agent. In the present invention, the dispersing agent can be appropriately selected from the conventionally known dispersing agents. As the dispersant, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric surfactant, a polyfluorinated system or a fluorine-based surfactant can be used. Among the surfactants, a polymer dispersant is preferred from the viewpoint of obtaining uniform and fine dispersion.

Examples of the polymer dispersant include (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts and (partial) ammonium of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid. a salt (partially) alkylamine salt; a (co)polymer of a hydroxyl group-containing unsaturated carboxylic acid ester such as a hydroxyl group-containing polyacrylate; a modified product; a polyurethane; an unsaturated polyamine; Oxyalkanes; long-chain polyamine phthalamide phosphates; polyethyleneimine derivatives [reacted by the reaction of poly(lower alkyleneimine) with a polyester containing a free carboxyl group, the obtained guanamine, the bases Polyallylamine derivative (select one or more of polyallylamine, three kinds of compounds such as a polyester having a free carboxyl group, a polycondensate or a copolycondensate of a polyamine or a decylamine (polyester phthalamide); A compound, a reaction product obtained by carrying out the reaction, and the like.

The polymer dispersant is preferably a polymer dispersant having a nitrogen atom and a metal atom in a main chain or a side chain from the viewpoint of allowing the color material to be appropriately dispersed and having good dispersion stability, and is particularly excellent in dispersibility. In view of the fact that the coating film is formed without depositing foreign matter and enhancing the luminance and contrast, it is more preferable to form a polymer dispersant from a polymer having a tertiary amine-containing repeating unit.

The repeating unit having a tertiary amine is a moiety having affinity with the above color material. A polymer dispersant composed of a polymer having a tertiary amine-containing repeating unit usually contains a repeating unit which is a moiety having affinity with a solvent. The polymer having a tertiary amine-containing repeating unit is particularly preferably one having a block portion composed of a repeating unit having a tertiary amine and having a solvent affinity from the viewpoint of excellent heat resistance and a high-thinness coating film. A block copolymer of a block portion.

The tertiary amine repeating unit may have a tertiary amine, and the tertiary amine may be contained in a side chain of the block polymer or may constitute a main chain.

Among them, a repeating unit having a tertiary amine is preferred, and a structure represented by the following general formula (I) is more preferable from the viewpoint that the main chain skeleton is not easily thermally decomposed and has high heat resistance:

(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 - a divalent organic group; R ³ and R ⁴ Each of them independently represents a chain or cyclic hydrocarbon group which may be substituted, or R ³ and R ⁴ are bonded to each other to form a cyclic structure. Each of R ⁵ and R ⁶ is independently a hydrogen atom or a methyl group.

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

The divalent linking group Q of the above general formula (I) may, for example, be an alkylene group having 1 to 10 carbon atoms, an extended aryl group, a -CONH- group, a -COO- group or an ether group having 1 to 10 carbon atoms ( -R'-OR"-: R' and R" are each independently an alkylene group) and combinations thereof. Among them, Q is preferably a -COO- group or a -CONH from the viewpoint of heat resistance of the obtained polymer, solubility of propylene glycol monomethyl ether acetate (PGMEA) which is preferably used as a solvent, and a relatively inexpensive material. -base.

The above-mentioned divalent organic group R ² of 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 optionally linear or branched, and examples thereof include a methylene group, a vinyl group, a trimethylene group, a propyl group, various butyl groups, various pentylene groups, and various kinds of extensions. Hexyl, various kinds of octyl groups, etc.

Each of R ⁵ and R ⁶ is independently a hydrogen atom or a methyl group.

The above R ^{2 is} preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility, and R ^{2 is more} preferably a methylene group, an ethyl group, a propyl group or a butyl group. It is a methylene group and an ethyl group.

In the above general formula (I), the cyclic structure in which R ³ and R ⁴ are bonded to each other may, for example, be a nitrogen-containing heterocyclic monocyclic ring having a five- to seven-membered ring or a condensation formed by the two condensations. ring. The nitrogen-containing heterocyclic ring is preferably not aromatic, and more preferably a saturated ring.

The repeating unit represented by the above general formula (I) may, for example, be dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate or diethylaminoethyl (meth)acrylate. (meth)acrylate containing an alkyl-substituted amino group such as diethylaminopropyl (meth)acrylate; dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (A) (meth) acrylamide containing an alkyl-substituted amine group such as acrylamide. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferred to use dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl ( Methyl) acrylamide.

In the block portion composed of the above-described tertiary amine repeating unit, the structural unit represented by the general formula (I) is preferably contained in three or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferably 3 to 100, more preferably 3 to 50, and particularly preferably 3 to 30.

a block copolymer having a block portion (hereinafter referred to as "B block") having a solvent affinity with a block portion (hereinafter referred to as "A block") composed of the above-described tertiary amine repeating unit, The solvent-affinity block portion has a structural unit represented by the above general formula (I) from the viewpoint of improving solvent affinity and improving dispersibility, but has copolymerization with the above general formula (I). A solvent affinity block that constitutes the unit. In the present invention, the block arrangement of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, from the viewpoint of excellent dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

The above B block is preferably the same as the B block of International Publication No. 2016/104493.

The number of constituent units constituting the solvent affinity block portion may be appropriately adjusted within a range in which the dispersibility of the color material can be improved. Among them, from the viewpoints that the solvent affinity portion and the color material affinity portion can effectively function and enhance the dispersibility of the color material, the number of constituent units constituting the solvent affinity block portion is preferably from 10 to 200, more preferably 10 ~100, especially good 10~70.

The solvent affinity block portion may be selected so as to exhibit the function of the solvent affinity site, and the repeating unit constituting the solvent affinity block portion may be composed of a single species or may contain two or more types of repeating units.

In the block copolymer used as the dispersing agent of the present invention, the number of units m of the structural unit represented by the above general formula (I) and the number n of units of other constituent units constituting the solvent affinity block portion are m/n, From the viewpoint of dispersibility of color material and dispersion stability, it is preferably in the range of 0.01 to 1 and more preferably in the range of 0.05 to 0.7.

Further, the dispersant of the present invention preferably contains a structure represented by the above general formula (I) and an amine from the viewpoint of good dispersibility, no precipitation of foreign matter upon formation of a coating film, and improvement in luminance and contrast. The polymer has a value of 40 mgKOH/g or more and 120 mgKOH/g or less.

When the amine value is within the above range, the viscosity is excellent in stability over time and heat resistance, and alkali developability and solvent resolubility are also excellent. When the amine value of the dispersing agent is high, the dispersibility and the dispersion stability are improved, the solvent solubility and the solvent resolubility are improved, the compatibility with other components is good, and the linearity of the fine line pattern of the colored layer is improved. It is easy to suppress the trembling of tiny holes. In the present invention, the amine value of the dispersant is particularly preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. 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 the amount of perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by a method defined in JIS-K7237. When measured by this method, even if an amine group is formed as a salt with an organic acid compound in a dispersing agent, since the organic acid compound is usually dissociated, the amine value of the block copolymer itself used as a dispersing agent can be measured.

The acid value of the dispersing agent used in the present invention is preferably 1 mgKOH/g or more from the viewpoint of the development residue suppressing effect. In particular, the acid value of the dispersant is more preferably 2 mgKOH/g or more from the viewpoint of further improving the development residue suppressing effect. Further, the acid value of the dispersant used in the present invention is an acid of a dispersant from the viewpoint of preventing deterioration of development adhesiveness and deterioration of solvent resolubility, improving the linearity of the fine line pattern of the colored layer, and easily suppressing the chattering of the micropore. The upper limit of the value is preferably 18 mgKOH/g or less. In particular, the acid value of the dispersant is preferably 16 mgKOH/g or less, and particularly preferably 14 mgKOH/g or less from the viewpoint of good development adhesion and solvent resolubility.

The dispersant used in the present invention preferably has a block copolymer acid value of 1 mgKOH/g or more, more preferably 2 mgKOH/g or more, before salt formation. The reason is that the development residue suppression effect can be improved. Further, 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 particularly preferably 14 mgKOH/g or less. The reason is that the development adhesiveness and the solvent resolubility are good.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C or more from the viewpoint of improving the development adhesion. That is, the glass transition temperature is preferably 30 ° C or higher regardless of the block copolymer before the formation of the dispersant salt or the salt block copolymer. If the glass transition temperature of the dispersant is low, particularly close to the developer temperature (usually about 23 ° C), there is a possibility that the development adhesiveness is lowered. The reason is that if the glass transition temperature is close to the developer temperature, the movement of the dispersant during development becomes large, and as a result, it is estimated that the development adhesiveness is deteriorated. When the glass transition temperature is 30° C. or higher, the movement of the dispersant molecules during development is suppressed, and it is estimated that the development adhesiveness is suppressed from being lowered.

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

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

Further, the glass transition temperature (Tg) of the block portion and the block copolymer can be calculated according to the following formula: 1/Tg = Σ (Xi / Tgi)

Here, the block portion is made to be copolymerized by n monomer components of i=1 to n. The weight fraction of the monomer No. i of the Xi system (ΣXi=1), and the glass transition temperature (absolute temperature) of the monomer of the Tgi-based monomer. However, the tether is set to the sum of i=1 to n. Further, the glass transition temperature of the homopolymer of each monomer of the value (Tgi) can be based ^{Polymer Handbook (3 rd Edition) (} J.Brandrup, EHImmergut the (Wiley-Interscience, 1989)) value.

When the concentration of the color material is increased and the content of the dispersant is increased, the amount of bonding is relatively reduced, so that the colored resin layer is more easily peeled off from the underlying substrate during development. The dispersing agent contains a B block which is a unit derived from a carboxyl group-containing monomer, and has the above specific acid value and glass transition temperature, whereby the development adhesiveness can be improved. When the acid value is too high, the developability is excellent, but the polarity is excessively high, and it is estimated that peeling easily occurs during development.

As described above, the dispersant of the present invention is excellent in dispersion stability of a color material, and is improved in contrast. When the colored resin composition containing the oxime ester compound represented by the above general formula (1) is formed, generation of development residue and solvent reactivity can be suppressed. From the viewpoint of being excellent in solubility and having high development adhesiveness, and preferably forming a micropore having excellent shape and easily suppressing micropore tremor and developing residue, the structure represented by the above general formula (I) is preferably included. Further, the polymer having an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less has an acid value of 1 mgKOH/g or more and 18 mgKOH/g or less, and a glass transition temperature of 30 °C or more.

As the above-mentioned carboxyl group-containing single system, a monomer which can be copolymerized with a monomer having a structural unit represented by the general formula (I) and which contains an unsaturated double bond and a carboxyl group can be used. Such a single system may, for example, be (meth)acrylic acid, vinyl benzoate, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamon Acid, acrylic acid dimer, and the like. Further, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a cyclic dehydrated product such as maleic anhydride, decanoic anhydride or cyclohexane dicarboxylic anhydride may be used. a reactant; or ω-carboxy-polycaprolactone mono(meth)acrylate or the like. Further, an acid anhydride group-containing monomer such as maleic anhydride of a carboxyl group, itaconic anhydride or citraconic anhydride may be used. Among these, (meth)acrylic acid is more preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

In the block copolymer before salt formation, the proportion of the constituent unit derived from the carboxyl group-containing monomer is appropriately set as long as the acid value of the block copolymer is within the specific acid value range, and there is no particular possibility. The total amount of the total constituent units of the block copolymer is preferably from 0.05% by mass to 4.5% by mass, more preferably from 0.07% by mass to 3.7% by mass.

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

In addition, the constituent unit derived from the carboxyl group-containing monomer may be one type or two or more types of constituent units as long as it can be the specific acid value.

In addition, from the viewpoint of setting the glass transition temperature of the dispersant used in the present invention to a specific value or more and improving the development adhesion, the monomer having a glass transition temperature (Tgi) of 10 ° C or more is obtained. The total amount in the B block is preferably 75% by mass or more, more preferably 85% by mass or more.

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

The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, and is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, and more preferably from 3,000 to 390 from the viewpoint of good dispersibility of color material and dispersion stability. 12000.

Here, the weight average molecular weight (Mw) is determined by a gel permeation chromatography (GPC) based on a standard polystyrene conversion value. Further, the macromonomer, the salt block copolymer, and the graft copolymer which are the raw materials of the block copolymer are also subjected to the above conditions.

Specific examples of the block copolymer having a block portion composed of such a tertiary amine repeating unit and a solvent-compatible block portion are preferably, for example, a block copolymer described in Japanese Patent No. 4911253 .

The polymer containing the above-mentioned tertiary amine repeating unit is used as a dispersing agent. When the coloring material is dispersed, the content of the polymer containing the tertiary amine repeating unit is preferably 15 mass with respect to 100 parts by mass of the color material. It is preferably -300 parts by mass, more preferably 20 parts by mass to 250 parts by mass. When it is in the above range, both the dispersibility and the dispersion stability are excellent, and the effect of improving the contrast is high.

In the present invention, from the viewpoint of dispersibility of color material and dispersion stability, it is also preferred to form a salt from at least a part of an amine group containing the above-mentioned tertiary amine repeating unit, an organic acid compound or a halogenated hydrocarbon. It is used as a dispersing agent (hereinafter, such a polymer is called "salt type polymer").

Among them, from the viewpoint of excellent dispersibility of color material and dispersion stability, it is preferred to contain a polymerization system block copolymer having a tertiary amine repeating unit, and the above organic acid compound is phenylphosphonic acid, phenyl An acidic organic phosphorus compound such as phosphonic acid. Specific examples of the organic acid compound to be used in the above-mentioned dispersing agent include an organic acid compound described in JP-A-2012-236882.

Further, the halogenated hydrocarbon is preferably at least one of a halogenated allyl group such as allyl bromide or chlorotoluene and a halogenated aralkyl group from the viewpoint of excellent dispersibility in color material and dispersion stability. 1 species.

In the case of using a dispersing agent, the content is not particularly limited as long as the coloring material can be uniformly dispersed. For example, 1% by mass of the total solid content of the photosensitive colored resin composition for a color filter can be used. ~40% by mass. Further, the total amount of the solid content of the photosensitive colored resin composition for a color filter is preferably blended in a ratio of 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass. . When it is more than the above lower limit value, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive coloring resin composition for a color filter is more preferable. Moreover, when it is below the said upper limit, the developability is favorable. In particular, when a coloring layer having a high concentration of a color material is formed, the amount of the dispersant is preferably from 2% by mass to 25% by mass based on the total amount of the solid content of the photosensitive colored resin composition for a color filter. The ratio of 3% by mass to 20% by mass of the best system is blended.

 [Antioxidants]  

The photosensitive colored resin composition for a color filter of the present invention may further contain an antioxidant. The photosensitive colored resin composition for a color filter of the present invention contains an antioxidant in combination with the oxime ester compound represented by the above general formula (1), thereby improving heat resistance and suppressing exposure and post-baking. Since the luminance is lowered, the luminance can be improved, and when the cured film forms minute pores, the hardening property is not impaired, and excessive radical chain reaction in the micropores can be controlled, so that minute pores of a desired shape can be formed more easily.

The antioxidant used in the present invention is not particularly limited, and can be appropriately selected from those known to those skilled in the art. Specific examples of the antioxidant include a hindered phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and a lanthanide-based antioxidant, and the viewpoint of heat resistance and fine pore shape are good. In particular, a hindered phenol-based antioxidant is preferably used.

The "hindered phenolic antioxidant" is an antioxidant having at least one phenol structure and having at least one of the hydroxy group at the 2-position and the 6-position, and having a substituent of 4 or more carbon atoms.

Specific examples of the hindered phenol-based antioxidant include dibutylhydroxytoluene (BHT) and neopentyltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid. Ester] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanate (trade name: IRGANOX 3114, 2,4,6-tris(4-hydroxy-3,5-di-t-butylbenzyl)-mesene (trade name: IRGANOX 1330, manufactured by BASF), 6-(4-hydroxy-3) ,5-di-t-butylanilino)-2,4-bis(octylthio)-1,3,5-three (trade name: IRGANOX 565, manufactured by BASF), 2,2'-thiodiethylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035, manufactured by BASF), 1,2-bis[3-(4-hydroxy-3,5-di-t-butylphenyl)propanyl]anthracene (trade name: IRGANOX MD1024, manufactured by BASF), 3- (4-Hydroxy-3,5-diisopropylphenyl)propionic acid octyl ester (trade name: IRGANOX 1135, manufactured by BASF), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX 1520L, manufactured by BASF), N,N'-hexamethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanamide] (trade name: IRGANOX 1098, BASF) , 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259, manufactured by BASF), 1-dimethyl -2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]ethyl]2,4,8,10-tetra Spiro[5.5]undecane (trade name: ADK STABA0-80, manufactured by ADEKA), bis(3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid) ethylene bis(oxyethylene) (trade name) :IRGANOX 245, manufactured by BASF), 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1 , 3,5-three -2,4,6(1H,3H,5H)-trione (trade name: IRGANOX 1790, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: SUMIRAIZA MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF), 3,5 -Diethyl tert-butyl-4-hydroxybenzylphosphonate (trade name: IRGAMOD 195, manufactured by BASF), 2-tert-butyl-4-methyl-6-(2-hydroxy-3) -T-butyl-5-methylbenzyl)phenyl ester (trade name: SUMIRAIZA GM, manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-thiobis(6-t-butyl-m-cresol) (trade name) : SUMIRAIZA WX-R, manufactured by Sumitomo Chemical Co., Ltd., 6,6'-di-tert-butyl-4,4'-butylene m-cresol (trade name: ADEKA STAB AO-40, manufactured by ADEKA). Other oligomeric and polymeric compounds which can also form a hindered phenol structure.

Further, in the present invention, a potential antioxidant can also be used as the antioxidant. The "potential antioxidant" of the present invention is a compound having a protective group which is detached by heating, and exhibits an antioxidant function by detachment of the protective group. Among them, it is preferable that the protective group is easily detached by heating at 150 ° C or higher. Since the latent antioxidant does not have an antioxidant function at the time of exposure, the radical generated by the photoinitiator is not deactivated, and the sensitivity reduction, the suppression of the line width thinning, and the improvement of the residual film ratio can be easily suppressed. On the other hand, in the heating step performed after the exposure, since the protective group is detached to exhibit an antioxidant effect, it is possible to suppress the occurrence of discoloration of the color material or the like, and a high-luminance colored layer can be obtained.

The latent antioxidant which is preferably used in the present invention is, for example, from the viewpoint of heat resistance and a fine pore shape, for example, a phenolic hydroxyl group of a hindered phenol-based antioxidant can be removed by heating. Specific examples of the potentially hindered phenol-based antioxidant to be protected include, for example, the following chemical formulas (a) to (c), but are not limited thereto.

Chemical formula (a)

The method for producing the above-mentioned latent antioxidant is not particularly limited, and for example, Japanese Patent Laid-Open Publication No. Sho 57-111375, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. The phenolic compound produced by the method described in each of JP-A-2004-501128 can be obtained by reacting with, for example, an acid anhydride, an acid chloride, a Boc reagent, a halogenated compound, a chlorosilane compound, an allyl ether compound or the like. Further, a commercially available product can also be used.

The protective group which is detached by heating may, for example, be an acid anhydride, an acid chloride, a Bocing agent, a halogenated compound, a chlorosilane compound, or a reactive residue of an allyl ether compound, and may be, for example, a third butoxy group. Carbonyl.

The content of the antioxidant is not particularly limited. For example, 0.1% by mass to 20% by mass based on the total amount of the solid content of the photosensitive colored resin composition for a color filter can be used. In addition, it is preferable to blend 0.2% by mass to 10% by mass based on the total amount of the solid content of the photosensitive colored resin composition for a color filter from the viewpoint of the effect of the use of the photoinitiator in combination. More preferably, the ratio is from 0.3% by mass to 5% by mass.

In addition, when the photosensitive colored resin composition for a color filter of the present invention further contains an antioxidant, the light used in the present invention is used from the viewpoint of sufficiently exhibiting the effect together with the photoinitiator. The total amount of the starting agent is preferably 100 parts by mass, more preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more.

On the other hand, the total amount of the photoinitiator used in the present invention is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, from the viewpoint of maintaining the appropriate sensitivity.

 [optional addition]  

The photosensitive coloring resin composition for a color filter may contain various additives as needed. The additive may, for example, be a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, a adhesion promoter, or the like.

Specific examples of the surfactant and the plasticizer are, for example, those described in JP-A-2013-029832.

The ratio (P) of the mass (P) of the color material used in the present invention to the mass (V) of the solid material other than the color material (hereinafter also referred to as "P/V ratio") is as long as the coloring layer of the color filter is formed. The remaining color is not particularly limited, and is preferably in the range of 0.05 or more and 1.00 or less, more preferably in the range of 0.10 or more and 0.80 or less, and particularly preferably in the range of 0.15 or more and 0.75 or less. Preferably, it is in the range of 0.20 or more and 0.70 or less. By setting the P/V ratio within the above range, it is possible to form a photosensitive coloring resin composition for a color filter which emits a desired coloring layer, and to form a photosensitive coloring resin for the color filter. The material can be uniformly dispersed.

When it is a red colored resin composition, P/V is preferably 0.50 or more, more preferably 0.60 or more, and particularly preferably 0.74 or more from the viewpoint of desired color development. Further, it is preferably 1.0 or less.

When the green colored resin composition is used, the P/V ratio is preferably 0.46 or more, more preferably 0.56 or more, and particularly preferably 0.68 or more from the viewpoint of desired color development. Further, it is preferably 1.0 or less.

When it is a blue colored resin composition, P/V is preferably 0.24 or more, more preferably 0.34 or more, and particularly preferably 0.41 or more from the viewpoint of desired color development. Further, it is preferably 1.0 or less. When the value is at least the above lower limit value, the color density of the photosensitive colored resin composition for a color filter can be increased, and the color filter pixel can have a higher color rendering and a lower film thickness. Moreover, when it is below the upper limit, it is excellent in storage stability, and the coloring layer which has sufficient hardness and the adhesiveness with a board|substrate is acquired.

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

The method for producing a photosensitive colored resin composition for a color filter of the present invention comprises a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent (preferably a dispersant), an antioxidant, and From the viewpoint of improving the contrast, it is preferred to use a dispersing agent to uniformly disperse the color material in a solvent, and to prepare by mixing using a known mixing means.

The method for preparing the resin composition is, for example, (1) first adding a color material and a dispersing agent to a solvent to prepare a color material dispersion, and then mixing the alkali-soluble resin, the photopolymerizable compound, and the dispersion into the dispersion; a photoinitiator and a method of adding various components as required; (2) simultaneously throwing in a solvent, a coloring material, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and optionally a method of adding various components and mixing; (3) adding, in a solvent, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives to be used as needed, and mixing, adding a method of dispersing a color material; (4) adding a color material, a dispersing agent, and an alkali-soluble resin in a solvent to prepare a color material dispersion, and further adding an alkali-soluble resin, a solvent, and photopolymerization to the dispersion A compound, a photoinitiator, and a method of mixing various additives as needed, and the like.

Among these methods, the methods (1) and (4) above are preferred from the viewpoint of effectively preventing aggregation of the color material and uniform dispersion.

The method of preparing the color material dispersion can be appropriately selected from the conventionally known dispersion methods. For example, (1) preparing a dispersant solution by mixing a dispersant in a solvent in advance and stirring, and then mixing the organic acid compound as needed to form a salt of the amine group of the dispersant with an organic acid compound, and then combining the color material with the color material. And mixing other components as needed, using a known mixer or disperser to perform dispersion; (2) mixing the dispersant in a solvent and stirring to prepare a dispersant solution, followed by color materials, optionally organic acid compounds, and optionally Mixing other components, using a known mixer or disperser; (3) mixing the dispersant in a solvent and stirring to prepare a dispersant solution, then mixing the color material and other components as needed, using a known blender or After the dispersion machine forms a dispersion, a method of adding an organic acid compound or the like as needed is employed.

Examples of the dispersing machine for performing the dispersion treatment include a roll mill such as a twin roll machine and a three roll machine; a ball mill such as a ball mill and a vibratory ball mill; a paint regulator, a continuous disc type bead mill, and a continuous ring type bead. Bead mills such as mills. The preferred dispersion conditions of the bead mill are preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

 II. Color filter  

The color filter of the present invention includes at least a substrate and a color filter provided with a colored layer on the substrate, wherein at least one of the colored layers is a photosensitive colored resin for the color filter of the present invention. a colored layer composed of a cured product of the composition.

The color filter of the present invention is described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention includes a substrate 1, a light blocking portion 2, and a coloring layer 3.

 (colored layer)  

At least one of the coloring layers used in the color filter of the present invention is a coloring layer composed of a cured product of the photosensitive colored resin composition for a color filter of the present invention.

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

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

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

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

First, the photosensitive coloring resin composition for a color filter of the present invention is coated by a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. A wet coating film is formed by coating on a substrate to be described later. Among them, a spin coating method or a die coating method is preferably used.

Then, the wet coating film is dried by a hot plate, an oven, or the like, and then exposed to a mask having a predetermined pattern, and an alkali-soluble resin and a photopolymerizable compound are photopolymerized to form a cured coating film. . Examples of the light source used for the exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted in accordance with the light source used, the thickness of the coating film, and the like.

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

Next, development processing is carried out using a developing solution, and by dissolving and removing the unexposed portion, a coating film is formed in a desired pattern. The developer is usually a solution in which an alkali is dissolved in water or a water-soluble solvent. An appropriate amount of a surfactant or the like may be added to the alkali solution.

Further, the development method can be carried out by a general method.

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

Further, when the color filter of the present invention is formed on a color filter on Array (COA) structure or the like, a micro hole may be formed in the colored layer when the development process is performed. . According to the present invention, since the photosensitive colored resin composition for a color filter described above is used, desired minute pores can be easily formed in the colored layer. The shape of the micropores is appropriately selected depending on the application, and is not particularly limited. The present invention can form micropores having a size of, for example, about 10 μm × 10 μm to 30 μm × 30 μm. Further, the shape of the minute holes is not particularly limited, and may be, for example, a circular shape, an elliptical shape, a polygonal shape or the like.

In the method of forming the minute holes in the colored layer, for example, a mask used for forming the color layer may be used, and in the opening pattern of the pattern mask capable of forming the thin line pattern, pattern light for forming a micro mask for the micro hole is disposed. The method of the cover.

 (lighting part)  

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

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape. The light-shielding portion can form a metal thin film such as chromium by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing a light-shielding particle such as carbon fine particles, a metal oxide, an inorganic pigment or an organic pigment in the resin binder. When the resin layer containing the light-blocking particles is used, for example, a method of patterning by development using a photosensitive photoresist, a method of patterning using an inkjet ink containing light-shielding particles, and heat application of the photosensitive photoresist can be employed. Transfer method, etc.

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

 (substrate)  

For the substrate, for example, a transparent substrate, a germanium substrate, and an aluminum, silver, silver/copper/palladium alloy thin film, or the like are formed on a transparent substrate or a germanium substrate. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on the substrates.

The transparent substrate of the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, for example, a transparent transparent material such as quartz glass, an alkali-free glass, or a synthetic quartz plate, or a transparent transparent resin such as a transparent resin film, an optical resin plate, or a flexible glass can be used. Characters.

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

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

 III. Display device  

The display device of the present invention is characterized by having the above-described color filter of the present invention. The configuration of the display device of the present invention is not particularly limited, and can be appropriately selected from known display devices such as a liquid crystal display device, an organic light-emitting display device, and the like.

 [Liquid Crystal Display Device]  

The liquid crystal display device is characterized by comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

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 a liquid crystal display device of the present invention. As shown 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 surface formed between the color filter 10 and the counter substrate 20. Liquid crystal layer 30.

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

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

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

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

The method of forming the liquid crystal layer may be a method used in a general liquid crystal cell fabrication method, such as a vacuum injection method, a liquid crystal dropping method, or the like. After the liquid crystal layer is formed by the above method, the liquid crystal cell can be aligned by gradually cooling the liquid crystal cell to a normal temperature.

 [Organic light-emitting display device]  

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

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

The method of laminating the organic light-emitting body 80 is, for example, a method of sequentially forming 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 on the color filter; A method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60 or the like. The transparent anode 71 of the organic light-emitting body 80, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 may be appropriately used. The organic light-emitting display device 100 thus produced can be applied to, for example, a passively driven organic EL display and an actively driven organic EL display.

Further, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and an organic light-emitting display device using a color filter is generally known.

 [Examples]  

Hereinafter, an exemplary embodiment of the present invention will be specifically described. However, the invention is not limited by the description.

The structure of the obtained compound was measured by 1H- and 13C-NMR mass spectrometry using a nuclear magnetic resonance apparatus (Bruker BioSpin, AVANCE III HD 500 MHz), and using a liquid chromatograph/mass spectrometer (Shimadzu Corporation, LC-30A, Bruker) The quality analysis of Daltonics and micrOTOFQ2) can be confirmed.

 (Synthesis Example 1: Synthesis of Compound A)    (1) Synthesis of intermediate A1  

0.60 mol of hydrazine, 2.4 mol of potassium hydroxide and 0.06 mol of potassium iodide were dissolved in 500 ml of anhydrous dimethyl hydrazine under nitrogen atmosphere, and maintained at 15 ° C. 1.33 mol of bromobutane was added slowly over 2 hours, and the reactant was at 15 ° C. Stir for 1 hour. Then, 2 L of distilled water was added to the reaction mixture and stirred for about 30 minutes, and then the product was extracted with 2 L of dichloromethane, and the extracted organic layer was washed twice with 2 L of distilled water. Then, the organic layer recovered was dried over anhydrous MgSO ₄ , and the solvent was subjected to distillation under reduced pressure to give a product, which was obtained by using a silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1:20). After purification, the following intermediate A1 was obtained.

 (2) Synthesis of intermediate A2  

The above intermediate A1 (0.11 mol) was dissolved in 500 ml of dichloromethane, and after cooling to -5 ° C, AlCl ₃ : 0.13 mol was slowly added, and the temperature of the reaction was not raised, and the mixture was slowly dropped for 1 hour. A solution of 15 ml of methyl chloride and 0.13 mol of cyclohexylpropionyl chloride was stirred at -5 ° C for 1 hour. Then, the reaction product was slowly poured into 500 ml of ice water, and after stirring for 30 minutes, the organic layer was washed with 200 mL of distilled water. Then, the collected organic layer was subjected to vacuum distillation to obtain a product, which was subjected to purification by a silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1:4) to obtain the following intermediate A2.

 (3) Synthesis of intermediate A3  

The above intermediate A2 (0.042 mol) was dissolved in 200 ml of tetrahydrofuran (THF), and sequentially dissolved in 1,4-di (4N)HCl in alkane: 25 ml and 0.063 mol of isobutyl nitrite, and the reaction was stirred at 25 ° C for 6 hours. Then, 200 ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes, and the organic layer was separated, and then washed with 200 ml of distilled water. Then, the organic layer which was collected was dried over anhydrous MgSO ₄ , and the solvent was distilled under reduced pressure to obtain a product, which was purified by a silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1:4). The following intermediate A3 was obtained.

[Chemistry 14]

 (4) Synthesis of Compound A  

The above intermediate A3 (0.056 mol) was dissolved in 200 ml of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, maintained at -5 ° C, and then added to a mixture of triethylamine (0.068 mol), and the reaction solution was stirred for 30 minutes. Then, a solution composed of 0.068 mol of chloroacetamidine and 10 ml of N-methyl-2-pyrrolidone was slowly added over 30 minutes, and the mixture was stirred for 30 minutes so that the reaction product did not rise. Then, 200 ml of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. Then, the organic layer which was collected was dried over anhydrous MgSO ₄ , and the solvent was distilled under reduced pressure to obtain a product. After recrystallization from 1 L of ethanol, the following compound A was obtained by drying.

 (Synthesis Example 2: Synthesis of Compound B)    (1) Synthesis of intermediate B1  

Except that in (1) of Synthesis Example 1, the bromobutane was replaced, and the ethyl bromide was used instead, and the purification was carried out without using a ruthenium tube chromatography, and the rest was in accordance with Synthesis Example 1. (1) Similarly, the following intermediate B1 was obtained.

 (2) Synthesis of intermediate B2  

Except for the intermediate A1 in the synthesis example 1, substituting the intermediate A1, the same intermediate B1 as the molar was used, and the cyclohexylpropionyl chloride was replaced, and the same molar alcohol was used instead. The following intermediate B2 was obtained in the same manner as in (2) of Synthesis Example 1.

 (3) Synthesis of intermediate B3  

Except for the intermediate A2 in the synthesis example 1, the intermediate B2 was replaced with the same molar, and the ruthenium column chromatography was replaced with ethyl acetate: n-hexane (1: The following intermediate B3 was obtained in the same manner as in (3) of Synthesis Example 1 except that the mixed solvent of 6) was subjected to recrystallization and dried.

 (4) Synthesis of Compound B  

The following compound B was obtained in the same manner as in the above (4) of Synthesis Example 1 except that the intermediate A3 was replaced with the above-mentioned intermediate B3.

 (Synthesis Example 3: Synthesis of Compound C)  

The following compound C was obtained in the same manner as in Synthesis Example 2 except that in the (2) of Synthesis Example 2, instead of the propionin chloride, the same procedure as in the synthesis of the butanyl chloride was used.

 (Synthesis Example 4: Synthesis of Compound D)    (1) Synthesis of intermediate D1  

0.030 mol of 9H-indol-2-yl-(phenyl)methanone was dissolved in 45 ml of dichloromethane, cooled to -5 ° C, and anhydrous AlCl _{3 was} added: 0.033 mol, and then 9 ml of dichloromethane and propional chloride 0.033 were added. The solution of mol was stirred slowly over 1 hour depending on the temperature of the reactants, and stirred at -5 ° C for 1 hour. Then, the reaction product was slowly poured into 250 g of ice water, and after stirring for 30 minutes, the organic layer was separated and washed with 100 ml of distilled water. Then, the collected organic layer was subjected to vacuum distillation to obtain a product, and recrystallization was carried out by using 20 ml of a mixed solution of toluene:ethyl acetate (5:1) to obtain the following intermediate D1.

 (2) Synthesis of intermediate D2  

The above intermediate D1 (0.010 mol) was dissolved in 30 ml of tetrahydrofuran (THF), and sequentially dissolved in 1,4-di (4N)HCl in the alkane: 4.5 ml, 0.015 mol with isoamyl nitrite, and the reaction was stirred at 25 ° C for 24 hours. Then, 20 ml of ethyl acetate and 50 ml of distilled water were added to the reaction solution to extract an organic layer. The organic layer to be extracted was dried over anhydrous MgSO ₄ , and the solvent was subjected to distillation under reduced pressure to obtain a product. Recrystallization was carried out using 30 ml of a mixed solvent of ethanol: ethyl acetate (5:1), followed by drying to obtain the following intermediates. D2.

 (3) Synthesis of Compound D  

The intermediate D2 (0.006 mol) was dissolved in 25 ml of ethyl acetate under a nitrogen atmosphere, the reaction product was maintained at -5 ° C, 0.007 mmol of triethylamine was added, and the reaction solution was stirred for 30 minutes, and the reaction product was not heated. A solution composed of 0.007 mol of chloroacetamidine and 5 ml of ethyl acetate was slowly added for 30 minutes, and stirred for 30 minutes. Then, 100 ml of distilled water was slowly added to the reaction mixture and stirred for about 30 minutes to separate the organic layer. Then, the recovered organic layer was dried over anhydrous MgSO ₄ to give the compound D below by subjecting solvent to distillation under reduced pressure.

Compound 23

 (Synthesis Example 5: Synthesis of Compound E)    (1) Synthesis of intermediate E1  

In a 500 ml four-necked flask, 0.2 mol of diphenyl sulfide, 0.22 mol of powdered AlCl ₃ and 150 ml of dichloroethane were added, stirred and poured into argon gas, and cooled to an ice bath. When the temperature dropped to 0 ° C, A solution of 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was started to be dropped, and the temperature was adjusted to 10 ° C or less, and it was added over about 1.5 hours. The temperature was raised to 15 ° C, and after stirring for 2 hours, the reaction liquid was discharged.

After diluting into 400 ml of ice and concentrated hydrochloric acid (65 ml) in dilute hydrochloric acid, the mixture was slowly stirred into the reaction solution, and the lower layer was separated by a separating funnel. The upper layer was extracted with 50 ml of dichloroethane, and the extract was separated from the lower layer. Liquid blending. Then, it was washed with a solution of NaHCO ₃ : 10 g and 200 g of NaHCO ₃ , and washed with 200 ml of water three times until the pH was neutral. After drying with 60 g of anhydrous MgSO ₄ , the water was removed and reused. Rotary evaporation evaporates the dichloroethane. The solid powder remaining in the rotary evaporation flask was placed in 200 ml of petroleum ether, subjected to suction filtration, and further poured into 150 ml of anhydrous alcohol, heated and refluxed. Thereafter, the mixture was cooled to room temperature, further cooled with ice for 2 hours, subjected to suction filtration, and dried in an oven at 50 ° C for 2 hours to obtain the following intermediate E1.

[Chem. 24] Intermediate E1

 (2) Synthesis of intermediate E2  

In a 500 ml four-necked flask, 42 g of the above intermediate E1, 400 g of tetrahydrofuran, 200 g of concentrated hydrochloric acid, and 24.2 g of isoamyl nitrite were added, and the mixture was stirred at room temperature for 5 hours, and then the reaction liquid was discharged.

The reaction solution was thrown into a large beaker, 1000 ml of water was added, and after stirring, it was allowed to stand overnight and layered to obtain a yellow viscous liquid. The viscous liquid was extracted with dichloroethane, dried (50 g of anhydrous MgSO _{4 )} , dried, and subjected to suction filtration, and the filtrate was subjected to rotary evaporation to remove the solvent to obtain an oily viscous material. Next, the dope was thrown into 150 ml of petroleum ether, and after stirring and precipitation, suction filtration was carried out to obtain a white powdery solid. Then, it was dried at 60 ° C for 5 hours to obtain the following intermediate E2.

 (3) Synthesis of Compound E  

In a 1000 ml four-necked flask, the above intermediate E2: 34 g, 350 ml of dichloroethane, and 12.7 g of triethylamine were added, stirred, and cooled in an ice bath. When the temperature was lowered to 0 ° C, the dropwise addition of chlorinated acetic acid was started. A solution of 15.7 g and 15 g of dichloroethane was added over about 1.5 hours. After stirring for 1 hour, 500 ml of cold water was dropped, and stratification was carried out using a separatory funnel. It was washed once with 200 ml of 5% NaHCO ₃ solution, and washed twice with 200 ml of water until the pH was neutral, and then washed once with diluted hydrochloric acid 20 g of concentrated hydrochloric acid and 400 ml of water, followed by use. After washing three times with 200 ml of water, it was dried over 100 g of anhydrous MgSO ₄ and the solvent was removed by rotary evaporation to obtain a viscous liquid. An appropriate amount of methanol was thrown into the viscous liquid to precipitate a white solid, which was filtered and dried to obtain the following compound E.

 (Synthesis Example 6: Synthesis of Compound F)  

Except that in (1) of Synthesis Example 5, the substituted diphenyl sulfide was replaced with [4-(phenylthio)phenyl]-2-thiophene-methanone of the same molar, and the others were synthesized and synthesized. In the same manner as in Example 5, the following compound F was synthesized.

[Chem. 27] Compound F

 (Synthesis Example 7: Production of Dispersant (Block Copolymer A))  

In a 500 mL round bottom four-port separable flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet tube, a mechanical agitator, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added. Nitrogen substitution was performed. After cooling the reaction flask to -60 ° C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Using an addition funnel for 60 minutes, 2.2 parts by mass of methic acid-1-ethoxyethyl ester (EEMA) of the B block monomer, and 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA) were dropped. 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and methyl methacrylate (MMA) 17.5 parts by mass. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) which is a monomer for the A block was dropped over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, vacuum-dried and purified, and diluted with PGMEA to obtain a 30% by mass solid solution. 32.5 parts by mass of water was added, the temperature was raised to 100 ° C, and the reaction was carried out for 7 hours, and the structural unit derived from EEMA was deprotected to form a constituent unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution is reprecipitated in hexane, and subjected to purification by filtration and vacuum drying to obtain an A block containing a structural unit represented by the general formula (I) and a constituent unit derived from a carboxyl group-containing monomer. Further, the solvating B block block copolymer A (acid value: 8 mgKOH/g, Tg: 38 ° C). The block copolymer A thus obtained was confirmed by GPC (gel permeation chromatography), and as a result, the weight average molecular weight Mw was 7730. Further, the amine value was 95 mgKOH/g.

 (Synthesis Example 8: Synthesis of alkali-soluble resin A solution)  

A mixed liquid of 40 parts by mass of styrene, 15 parts by mass of MMA, 25 parts by mass of MAA, and 3 parts by mass of AIBN under a nitrogen stream, and dropped into a PGMEA: 150 parts by mass at 100 ° C for 3 hours. In the slot. After the completion of the dropwise addition, the mixture was further heated at 100 ° C for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7,000.

Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heated at 110 ° C for 10 hours. The air is foamed in the solution. The obtained alkali-soluble resin A was introduced into a main chain formed by copolymerization of styrene MMA and MAA, and a resin having a side chain of an ethylenic double bond was introduced by using GMA, and the solid content was 42.6 mass%, and the acid value was 74 mgKOH/g. The weight average molecular weight is 12,000. The weight average molecular weight was measured using Shodex GPC System-21H using polystyrene as a standard material and THF as an eluent. Further, the acid worthy measurement method was measured in accordance with JIS K 0070.

 (Synthesis Example 9: Synthesis of blue color material α)    (1) Synthesis of Intermediate 1  

According to the production method of the intermediate 3 and the intermediate 4 described in International Publication No. 2012/144521, 1:15.9 g (yield 70%) of the intermediate represented by the following chemical formula (1) is obtained.

The obtained compound was confirmed to be a target compound by the following analysis.

‧MS(ESI)(m/z): 511(+), 2 price

‧ Elemental analysis values: CHN measured values (78.13%, 7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)

 (2) Synthesis of blue color material α  

15.00 g (4.58 mmol) of the above intermediate was added to 300 ml of water, and dissolved in an intermediate 1 solution at 90 °C. Next, 10.44 g (3.05 mmol) of phosphotungstic acid ‧n hydrate H ₃ [PW ₁₂ O ₄₀ ]‧nH ₂ O (n=30) (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was thrown into 100 ml of water, and stirred at 90 ° C An aqueous solution of phosphotungstic acid is prepared. In the immediately-prepared intermediate 1 solution, the prepared aqueous solution of phosphotungstic acid was mixed at 90 ° C, and the resulting precipitate was collected by filtration and washed with water. The obtained filter cake was dried to obtain a blue color material α: 13.25 g of a metal lake color material of the triarylmethane-based basic dye represented by the following chemical formula (2).

The obtained compound was confirmed to be a target compound by the following analysis.

‧MS(ESI)(m/z): 510(+), 2 price

‧ Elemental analysis values: CHN measured values (41.55%, 5.34%, 4.32%); theoretical values (41.66%, 5.17%, 4.11%)

 (Synthesis Example 10: Preparation of Azo Derivative 1)  

In 550 g of distilled water, 23.1 g of diazo barbituric acid and 19.2 g of barbituric acid were introduced. Subsequently, it was adjusted to become azo barbituric acid (0.3 mol) using an aqueous potassium hydroxide solution, and mixed with 750 g of distilled water. 5 g of 30% hydrochloric acid was added by dropping. Then, 38.7 g of melamine was introduced. Next, a 0.39 molar nickel chloride solution and a 0.21 molar zinc chloride solution were mixed and added, and stirred at a temperature of 80 ° C for 8 hours. The pigment was isolated by filtration, washed, dried at 120 ° C, and ground in a mortar to obtain Azo derivative 1 (Ni-azo-1, Ni:Zn = 65:35 (mole ratio) azo pigment).

 (Synthesis Example 11: Preparation of Azo Derivative 2)  

In addition to the preparation of the Azo derivative 1 of Synthesis Example 10, the 0.39 molar nickel chloride solution was replaced with the 0.21 molar zinc chloride solution, and the 0.42 molar nickel chloride solution and the 0.18 molar zinc chloride solution were used instead. The Azo derivative 2 (Ni-azo-2, Ni:Zn=70:30 (mole ratio) azo pigment) was obtained in the same manner as in Synthesis Example 10.

 (Synthesis Example 12: Preparation of Azo Derivative 3)  

In addition to the preparation of the Azo derivative 1 of Synthesis Example 10, a 0.39 molar nickel chloride solution was replaced with a 0.21 molar zinc chloride solution, and a 0.3 molar nickel chloride solution and a 0.3 molar zinc chloride solution were used instead. The Azo derivative 3 (Ni-azo-3, Ni:Zn = 50:50 (mole ratio) azo pigment) was obtained in the same manner as in Synthesis Example 10.

 (Synthesis Example 13: Preparation of Azo Derivative 4)  

In addition to the preparation of the Azo derivative 1 of Synthesis Example 10, instead of the 0.39 molar nickel chloride solution and the 0.21 molar zinc chloride solution, a 0.18 molar nickel chloride solution and a 0.42 molar zinc chloride solution were used instead. The Azo derivative 4 (Ni-azo-4, Ni:Zn=30:70 (mole ratio) azo pigment) was obtained in the same manner as in Synthesis Example 10.

 (Synthesis Example 14: Preparation of Azo Derivative 5)  

In addition to the preparation of the Azo derivative 1 of Synthesis Example 10, instead of the 0.39 molar nickel chloride solution, and the 0.21 molar zinc chloride solution, a 0.06 molar nickel chloride solution and a 0.54 molar zinc chloride solution were used instead. The Azo derivative 5 (Ni-azo-5, Ni:Zn = 10:90 (mole ratio) azo pigment) was obtained in the same manner as in Synthesis Example 10.

 (Synthesis Example 15: Synthesis of latent antioxidant (compound a))  

0.01 mol of the phenol compound represented by the following chemical formula (3), 0.05 mol of dibutyl butyl carbonate, and 30 g of pyridine were mixed, and 0.025 mol of 4-dimethylaminopyridine was added at room temperature under a nitrogen atmosphere. Stir at °C for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added thereto to carry out oil-water separation. The organic layer was dried over anhydrous sodium sulfate, the solvent was evaporated, and 100 g of methanol was added to the residue to carry out crystallization. The obtained white powdery crystals were dried under reduced pressure at 60 ° C for 3 hours to obtain a latent antioxidant (compound a) represented by the above formula (a). In addition, the structure of the latent antioxidant obtained was confirmed by IR and NMR.

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

The block copolymer A of the synthesis example 7 of the dispersing agent: 5.1 parts by mass, the blue color material α obtained by the synthesis example 9 of the color material: 13.0 parts by mass, and the alkali-soluble resin A solution obtained in Synthesis Example 8 were converted according to the solid content. 5.1 parts by mass, PGMEA: 76.8 parts by mass, and 100 parts by mass of 2.0 mm zirconia balls were placed in a milk bottle and shaken for 1 hour using a paint shaker (made by Asada Iron Works Co., Ltd.). Pre-crushing, and then taking out a zirconia ball having a particle diameter of 2.0 mm, adding 200 parts by mass of a zirconia ball having a particle diameter of 0.1 mm, and similarly using a paint shaker to perform formal disintegration for 4 hours to obtain a color material dispersion. 1.

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

Addition: 1:286.1 parts by mass of the color material dispersion obtained in the above (1), and 8.6 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 8 in terms of solid content, and a photopolymerizable compound (trade name: Aronix M-520D, East Asia) 18.2 parts by mass of a compound, a dibutylhydroxytoluene (BHT) of an antioxidant: 2.0 parts by mass, a compound A obtained by synthesizing the first initiator: 5.1 parts by mass, and PGMEA: 42.2 parts by mass, A photosensitive colored resin composition 1 for a color filter was obtained.

 (Examples 2 to 13)  

In the first embodiment, the photosensitive coloring resin compositions 2 to 13 for color filters were obtained in the same manner as in Example 1 except that the types and amounts of the materials shown in Table 1 were used.

Further, in Example 8, an OXE-01 oxime ester photoinitiator (trade name: IRGACURE OXE-01, manufactured by BASF) for use as a photoinitiator, a compound represented by the following chemical formula (4): ]

 (Example 14)  

In the same manner as in Example 13, except that BHT was not used for the antioxidant, and the bisphenol-based antioxidant (ADEKA STAB AO-40, manufactured by ADEKA) was used instead, the color filter for the color filter was obtained in the same manner as in Example 13. Sexually colored resin composition 14.

 (Example 15)  

A photosensitive colored resin composition for a color filter was obtained in the same manner as in Example 13 except that the antioxidant was not used in the case of the antioxidant, and the hindered phenol-based antioxidant (Irg 1010, manufactured by BASF) was used instead. 15.

 (Embodiment 16)  

In the same manner as in Example 13, except that the antioxidant was used in the same manner as in Example 13, except that the antioxidant was used without using BHT, the photosensitive coloring of the color filter was obtained in the same manner as in Example 13. Resin composition 16.

 (Examples 17 to 21)  

In the same manner as in Example 1, except that the amounts of the alkali-soluble resin, the photopolymerizable compound, the photoinitiator, and the antioxidant were changed as shown in Table 1, the color filter was obtained in the same manner as in Example 1. The photosensitive resin composition for filming is 17 to 21.

 (Comparative examples 1 to 3)  

Except that in Example 21, the photoinitiator was used in the same manner as in Example 21 except that the compound A obtained in Synthesis Example 1 was used instead of the photoinitiator shown in Table 1. Photosensitive resin compositions 1 to 3 were used.

The photoinitiator used in Comparative Example 1 is OXE-02 (manufactured by BASF) represented by the following chemical formula (5):

The photoinitiator used in Comparative Example 3 is a comparative compound A represented by the following chemical formula (6):

 (Example 22)  

In Example 13, except that the color material was replaced with the blue color material α, and the pigment red 254 (PR254) was used instead of 37.2 parts by mass, the photosensitive coloring for the color filter was obtained in the same manner as in Example 13. Resin composition 22.

 (Comparative Example 4)  

In the example 22, the compound A obtained in Synthesis Example 1 and the compound E obtained in Synthesis Example 5 and Irg 819 (manufactured by BASF) were used instead of the photoinitiator, and the above chemical formula (5) was used in the amounts shown in Table 2. OXE-02 (manufactured by BASF) was used, and photosensitive coloring for comparative color filters was obtained in the same manner as in Example 22 except that the antioxidant (BHT) was not used and 20.2 parts by mass of the photopolymerizable compound was used instead. Resin composition 4.

 (Example 23)  

In Example 13, except that the color material was substituted for the blue color material α, and 16.48 parts by mass of the pigment green 59 (PG59) and 1:20.72 parts by mass of the Azo derivative obtained in the synthesis example 10 were used instead, In the same manner as in Example 13, a photosensitive colored resin composition 23 for a color filter was obtained.

 (Comparative Example 5)  

In the same manner as in Example 23, the compound A obtained in Synthesis Example 1 and the compound E obtained in Synthesis Example 5 and Irg 819 (manufactured by BASF) were used, and the above chemical formula (5) was used instead. OXE-02 (manufactured by BASF) was used, and photosensitive coloring for comparative color filters was obtained in the same manner as in Example 23 except that the antioxidant (BHT) was not used and the photopolymerizable compound was used in an amount of 20.2 parts by mass. Resin composition 5.

 (Example 24)  

Except that in Example 13, the color material was replaced with the blue color material α, instead of using CI solvent yellow 162: 37.2 parts by mass, and no antioxidant (BHT) was used, and the photopolymerizable compound was used instead of 20.2 parts by mass. In the same manner as in Example 13, the photosensitive colored resin composition 24 for a color filter was obtained.

 (Comparative Example 6)  

In the same manner as in Example 24, the photoinitiator was not used in the compound A obtained in Synthesis Example 1, the compound E obtained in Synthesis Example 5, and the Irg 819 (manufactured by BASF), but in the amounts shown in Table 2, the above chemical formula (5) was used. The photosensitive colored resin composition 6 for comparison color filters was obtained in the same manner as in Example 24 except that OXE-02 (manufactured by BASF) was used.

 (Embodiment 25)  

Except that in Example 16, the color material was replaced with the blue color material α, and instead of using pigment green 58: 23.8 parts by mass and the Azo derivative obtained in Synthesis Example 11 2: 13.4 parts by mass, the rest were carried out in accordance with In the same manner as in Example 16, a photosensitive colored resin composition 25 for a color filter was obtained.

 (Example 26)  

Except that in Example 16, the color material was replaced with the blue color material α, and instead of using pigment green 58: 24.5 parts by mass and the Azo derivative obtained in Synthesis Example 12: 32.7 parts by mass, the rest was in accordance with Example 16. The photosensitive colored resin composition 26 for a color filter is obtained in the same manner.

 (Example 27)  

Except in Example 16, the color material was replaced with the blue color material α, and instead of using pigment green 58: 25.3 parts by mass and the Azo derivative obtained in Synthesis Example 13 4: 11.9 parts by mass, the rest were in accordance with the examples. In the same manner, the photosensitive colored resin composition 27 for a color filter is obtained in the same manner.

 (Embodiment 28)  

Except that in Example 16, the color material was replaced with the blue color material α, and instead of the pigment green 58:26.1 parts by mass and the Azo derivative obtained in Synthesis Example 14: 5:11.1 parts by mass, the rest were in accordance with the examples. In the same manner, the photosensitive colored resin composition 28 for a color filter is obtained in the same manner.

 (Example 29)  

The photosensitive colored resin composition 29 for color filters was obtained in the same manner as in Example 27 except that the antioxidant was used in place of the compound a and the BHT was used instead.

 (Embodiment 30)  

A photosensitive colored resin composition for a color filter was obtained in the same manner as in Example 27 except that the compound a of the antioxidant was not used, and the photopolymerizable compound was used in an amount of 0.22 parts by mass. 30.

 (Comparative Example 7)  

In the Example 27, the photoinitiator was not used in the compound A obtained in Synthesis Example 1, the compound E obtained in Synthesis Example 5, and the Irg 819 (manufactured by BASF), but the chemical formula (5) was used in the amounts shown in Table 2. The OXE-02 (manufactured by BASF) was used, and the photosensitive colored resin composition for comparative color filters was obtained in the same manner as in Example 27 except that the antioxidant was not used and the photopolymerizable compound was used in an amount of 20.2 parts by mass. 7.

 [Evaluation]  

The photosensitive colored resin composition obtained in each of the examples and the comparative examples was applied to a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater, and the thickness of the cured coating film was 3.0 μm. After coating, a hot film was applied and dried at 80 ° C for 3 minutes to form a coating film on the glass substrate. The coating film was placed with a 20 μm × 20 μm chrome mask pattern mask (chrome mask) in the center of the independent thin line having an opening size of 90 μm × 300 μm, and exposed to an ultraviolet light of 40 mJ/cm ² using an ultrahigh pressure mercury lamp. On the glass substrate, a post-exposure coating film is formed. Next, a 0.05 wt% potassium hydroxide aqueous solution was used as a developing solution, and spin coating development was carried out, and after contact with the developing solution for 60 seconds, it was washed with pure water and subjected to development treatment to obtain an independent fine line pattern coating film having minute pores. . Then, post-baking was performed for 25 minutes using a 230 ° C clean oven to form a separate thin line pattern-like colored layer having minute pores. The following evaluation was performed for the obtained colored layer.

 <Optical characteristic evaluation>  

The photosensitive colored resin composition obtained in each of the examples and the comparative examples was applied to a glass substrate ("NA35" manufactured by NH Techno Glass Co., Ltd.) using a spin coater, and then a heating plate was used. After drying at ° C for 3 minutes, a coating film was formed on the glass substrate. The 60 μJ/cm ² ultraviolet ray was completely irradiated with an ultrahigh pressure mercury lamp without a photomask to form a film after exposure. Next, a 0.05 wt% potassium hydroxide aqueous solution was used as a developing solution, and spin coating development was carried out. After the developer was contacted for 60 seconds, it was washed with pure water and subjected to development treatment to form a coating film after development. Then, after 25 minutes of post-baking in a 230 ° C clean oven, the chromaticity is y = 0.083 when using the blue color material α, and becomes x = 0.650 when using PR254, when using PG59 / Azo The derivative was y = 0.610, and when the CI solvent yellow 162 was used, it was y = 0.53, and when the PG58/Azo derivative was used, the hardened coating film (colored layer) was formed in such a manner as to be y = 0.630. The chromaticity (x, y) and the luminance (Y) of the colored layer were measured using an Olympus microspectrophotometry apparatus OSP-SP200.

 <Developability evaluation>    [linearity]  

The width of the thin line pattern of the coloring layer which was touched by the aperture width of 90 μm of the chrome mask used for the exposure was measured by optical microscopy, and the linearity was evaluated according to the variation of the line width.

A: The variation is within ±0.1μm

B: The variation exceeds ±0.1μm and is within ±0.3μm

C: Change exceeds ±0.3μm

 [residual film rate]  

When the colored layer is formed, the film thickness (E) after exposure and the film thickness (D) after development are measured by a stylus profiler P-16 (manufactured by KLA-Tencor Co., Ltd.) during the formation of the coating film. The film thickness (D) after development and the film thickness (E) after exposure were set as the residual film ratio and calculated.

Further, if the film thickness (D) after development or the film thickness (E) after exposure is 90% or more, it is suitable for practical use.

The colored layer was observed with an optical microscope, and the shape, tremor, and development residue of the micropore were evaluated in accordance with the following evaluation criteria.

 [shape]  

A: The size deviation of the micro holes formed on the colored layer relative to the size of the chrome mask disposed in the individual fine line pattern is less than 2% in absolute value

B: the size deviation of the micropores formed on the colored layer with respect to the size of the chrome mask disposed in the individual fine line pattern, which is 2% or more and less than 6% in absolute value

C: the size deviation of the minute holes formed on the colored layer with respect to the size of the chrome mask disposed in the independent thin line pattern, which is greater than 6% and less than 8% in absolute value

D: the size deviation of the micro holes formed on the colored layer relative to the size of the chrome mask disposed in the individual fine line pattern, greater than 8% in absolute value

In addition, the size offset calculates the average of the offsets of the sides.

 [shake]  

A: The ten-point average roughness of the peripheral portion of the minute hole formed on the colored layer is less than 0.1

B: The ten-point average roughness of the peripheral portion of the minute hole formed on the colored layer is 0.1 or more and 0.5 or less

C: The ten-point average roughness of the peripheral portion of the minute hole formed on the colored layer is greater than 0.5

In addition, the ten point average roughness was measured in accordance with JIS B0601.

 [Development residue]  

AA: When observed by an optical microscope, no coloration was observed inside the micropores formed on the colored layer, and no transparency was observed in the periphery of the micropores.

A: When observed by an optical microscope, although no coloration was observed inside the micropores formed on the colored layer, a transparent matter was observed at a part of the periphery of the micropore.

B: When observed by an optical microscope, coloring was observed inside the micropores formed on the colored layer.

The abbreviations in Table 1 and Table 2 are as follows:

‧ OXE-01: oxime ester photoinitiator (trade name: IRGACURE OXE-01, BASF)

‧ OXE-02: oxime ester photoinitiator (trade name: IRGACURE OXE-02, BASF)

‧Irg369: α-Aminoketone photoinitiator (IRGACURE 369, manufactured by BASF)

‧Irg907: α-amine ketone photoinitiator (IRGACURE 907, manufactured by BASF)

‧巯: 巯-chain transfer agent (2-mercaptobenzothiazole, Tokyo Chemical Industry)

‧Diimidazole: Diimidazole-based photoinitiator (HABI, black gold chemical system)

‧DETX: Oxygen and sulfur Photoinitiator (DOUBLECURE DETX, manufactured by Double Bond Chemical)

‧Irg819: bismuth phosphine oxide photoinitiator (IRGACURE 819, manufactured by BASF)

‧BHT: Dibutylhydroxytoluene

‧AO-40: Bisphenol-based antioxidant (ADEKA STAB AO-40, made by ADEKA)

‧Irg1010: Hindered phenolic antioxidant (IRGACURE 1010, manufactured by BASF)

 <Result finishing>  

The photoinitiator is a photosensitive colored resin composition of Examples 1 to 30 containing the above-described oxime ester compound represented by the general formula (1), as compared with a comparative photosensitive colored resin composition using the same color material, respectively. It is known that a coloring layer with enhanced brightness can be formed. Further, in the colored resin compositions of Examples 1 to 30, the residual film ratio was high and the sensitivity was good. In the photosensitive colored resin compositions of Examples 1 to 30, it was found that the fine line pattern was excellent in linearity, and when the colored layer was patterned, it was easy to form desired minute holes on the colored layer at the same time. Further, in Examples 1 to 3 in which the oxime ester compound in which Z of the above general formula (1) is a hydrogen atom, both the luminance and the residual film ratio are high; and Z using the above general formula (1) is -(C=O) In Example 4 of the oxime ester compound of R ^d , the oxime ester compound has better solvent solubility and compatibility with other components, and the shape of the minute pores is more excellent. Comparing the micropore cross sections of Example 1 and Example 2, the push-out angle of Example 2 was moderated, and the shape of the micro-holes was better.

Further, by using the oxime ester compound represented by the above general formula (1) and the oxime ester compound having a diphenyl sulfide skeleton in combination with a photoinitiator, the shape of the micropores is better (Example 1 and Examples) Comparison of 5 and comparison between Example 2 and Examples 6-8).

Further, the photoinitiator is used in combination with the oxime ester compound represented by the above general formula (1), the oxime ester compound having a diphenyl sulfide skeleton, and the α-amine ketone photoinitiator and the diimidazole system. Photoinitiator, oxygen sulfur When at least one selected from the group consisting of a photoinitiator, a phosphine oxide-based photoinitiator, and a quinone-based chain transfer agent, the linearity of the fine line pattern is improved, and the shape of the micropores is better (Example 5 and Comparison of Examples 9 to 13).

Further, by containing an antioxidant, the micropore tremor was further suppressed, and the luminance was also improved (comparison between Example 1 and Example 21, and Examples 27 and 29 and Example 30). When a latent antioxidant (compound a) is used from the antioxidant, the tremor of the micropore can be further suppressed, and the residual film ratio is as good as that in the case where the antioxidant is not used. On the other hand, when a latent antioxidant is not used but a hindered phenol-based antioxidant is used, the luminance can be more improved than in the case of using a latent antioxidant (comparison of Examples 27 and 29 with Example 30).

On the other hand, the photoinitiator did not contain the oxime ester compound represented by the above general formula (1), but Comparative Example 1 and Comparative Examples 4 to 7 using an oxime ester compound having a carbazole skeleton, as compared with the use of the same In the example of the color material, the difference in luminance and the linearity of the fine line pattern are poor, and microscopic holes cannot be formed.

Further, the photoinitiator did not contain the oxime ester compound represented by the above general formula (1), but Comparative Example 2 using Irg907 (α-amine ketone photoinitiator) was inferior in luminance and residual film ratio.

The photoinitiator does not contain the above-described oxime ester compound of the general formula (1), but a comparative example of a comparative compound A in which a fluorene skeleton has a nitro group and a carbonyl group is not bonded to the oxime skeleton via an oxime ester group. 3, the brightness and linearity are both poor. The reason why the linearity of Comparative Example 3 was poor was estimated to be because the solvent solubility of Comparative Compound A was poor and the compatibility with other components was poor.

Claims (12)

A photosensitive colored resin composition for a color filter, comprising: a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent; and the photoinitiator comprises the following general formula (1); Deuterated ester compound: (In general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group; and R ^c may also contain a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond ( a hydrocarbon group of at least one divalent linking group selected from -CO-); a Z-based hydrogen atom or -(C=O)R ^d ; and a R ^d system may further contain at least one selected from the group consisting of an oxygen atom and a sulfur atom The hydrocarbon group or a heterocyclic group which does not contain a nitrogen atom and contains at least one selected from the group consisting of an oxygen atom and a sulfur atom; and R ^e is a hydrocarbon group having 1 to 10 carbon atoms).  The photosensitive coloring resin composition for a color filter according to claim 1, wherein the photoinitiator contains two or more oxime ester compounds having no carbazole skeleton.    The photosensitive coloring resin composition for a color filter according to claim 1 or 2, wherein the photoinitiator further contains an oxime ester compound having a diphenyl sulfide skeleton.   The photosensitive coloring resin composition for a color filter according to claim 1 or 2, wherein the photoinitiator further comprises an optical starting from an α-aminoketone photoinitiator or a biimidazole photon. Agent, oxygen and sulfur At least one selected from the group consisting of a photoinitiator, a deuterated phosphine oxide photoinitiator, and a hydrazine chain transfer agent. The photosensitive coloring resin composition for a color filter according to claim 1, wherein the photoinitiator further comprises: an α-aminoketone photoinitiator, a diimidazole photoinitiator, and oxygen sulfur. At least one selected from the group consisting of a photoinitiator, a deuterated phosphine oxide photoinitiator and a lanthanide chain transfer agent; and an oxime ester compound having a diphenyl sulfide skeleton.  A photosensitive colored resin composition for a color filter according to claim 1 or 5, which further contains an antioxidant.    The photosensitive colored resin composition for a color filter according to claim 6, wherein the antioxidant is at least one selected from the group consisting of a hindered phenol antioxidant and a latent hindered phenol antioxidant; The hindered phenol-based antioxidant protects the phenolic hydroxyl group of the hindered phenol-based antioxidant by a protecting group which can be removed by heating.   The photosensitive colored resin composition for a color filter according to claim 1, further comprising a dispersant containing a polymer having a structure represented by the following general formula (I) and an amine value It is 40 mgKOH/g or more and 120 mgKOH/g or less: (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 )-CH (R ⁶ )-O] _x -CH(R ⁵ )-CH(R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group; R ³ And R ⁴ each independently represent a chain or cyclic hydrocarbon group which may be substituted, 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 a hydrogen atom or a methyl group; An integer from 1 to 18; y is an integer from 1 to 5; z is an integer from 1 to 18).  The photosensitive colored resin composition for a color filter according to claim 8, wherein the dispersant contains a polymer having a structure represented by the above general formula (I) and having an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less. And the acid value is 1 mgKOH/g or more and 18 mgKOH/g or less.    The photosensitive coloring resin composition for a color filter according to claim 1 or 8, wherein the color material contains a zinc phthalocyanine pigment and a yellow color material; the yellow color material contains: from the following general formula (ii) The at least one anion selected from the group consisting of mono-, di-, tri-, and tetra-anions of the azo compound and its tautomeric structure, and from Cd, Co, Al, Cr, Sn, Pb, At least two metal ions selected from the group consisting of Zn, Fe, Ni, Cu, and Mn.    A color filter comprising at least a substrate and a coloring layer provided on the substrate; at least one of the colored layers is a photosensitive coloring resin composition for a color filter according to any one of claims 1 to 10. a colored layer of cured material.    A display device having the color filter of the above-mentioned claim 11.