CN109642971B

CN109642971B - Photosensitive colored resin composition for color filter, and display device

Info

Publication number: CN109642971B
Application number: CN201780052979.9A
Authority: CN
Inventors: 铃木琢实; 大庭正干; 田尻亘; 山县秀明
Original assignee: DNP Fine Chemicals Co Ltd
Current assignee: DNP Fine Chemicals Co Ltd
Priority date: 2016-09-30
Filing date: 2017-09-25
Publication date: 2022-07-12
Anticipated expiration: 2037-09-25
Also published as: WO2018062105A1; JPWO2018062105A1; TW201818154A; JP7008508B2; TWI742166B; CN109642971A

Abstract

The invention provides a photosensitive coloring resin composition for a color filter, which can form a coloring layer with improved brightness and has good sensitivity. The photosensitive coloring resin composition for the color filter comprises a coloring material, an alkali soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, wherein the photoinitiator contains an oxime ester compound shown in a general formula (1). General formula (1)

Description

Photosensitive colored resin composition for color filter, and display device

Technical Field

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

Background

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays is increasing. The popularity of mobile displays (mobile phones, smart phones, tablet computers) is also increasing, and the market for liquid crystal displays is expanding day by day. In addition, recently, organic light emitting display devices such as organic EL displays that emit light and have high visibility have attracted attention as a next-generation image display device. Further improvement in image quality and reduction in power consumption of these image display devices are strongly desired.

Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in color image formation of a liquid crystal display device, light passing through a color filter is directly colored into colors of pixels constituting the color filter, and the colors of light are synthesized to form a color image. As a light source in this case, there is a case where an organic light emitting element which emits white light or an inorganic light emitting element which emits white light is used in addition to a known cold cathode tube. In addition, in the organic light emitting display device, a color filter is used for color adjustment and the like.

In recent years, there has been a demand for power saving of image display devices, and in particular, for higher luminance of color filters in order to improve the utilization efficiency of backlights. Especially, it is a major problem in mobile displays (mobile phones, smart phones, tablet PCs).

Here, the color filter generally has: a substrate; a colored layer formed on the substrate and including a colored pattern of three primary colors of red, green, and blue; and a light shielding portion formed on the substrate so as to partition each of the colored patterns.

As a method for forming a colored layer of a color filter, for example, a colored resin composition is prepared by adding a binder resin, a photopolymerizable compound and a photoinitiator to a color material dispersion liquid in which a color material is dispersed by a dispersant or the like, and the colored resin composition is applied onto a glass substrate and dried, then exposed to light using a photomask and developed to form a colored pattern, and the pattern is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.

When the demand for higher brightness of the color filter is increased, the color material concentration of the color filter coloring layer is increased, which results in a relatively smaller amount of components necessary for photopolymerization and makes patterning difficult. In addition, in order to improve productivity of the color filter, it is required to reduce cumulative exposure amount required for patterning, but how to ensure curability required for patterning becomes a big problem.

As a method for obtaining a colored resin composition capable of realizing high sensitivity, use of an oxime ester photoinitiator has been proposed. For example, patent document 1 proposes: an oxime ester compound having a carbazole skeleton and having a specific structure. Further, patent document 2 proposes: an oxime ester fluorene compound having a specific structure in which an oxime ester group is not bonded to a fluorene skeleton via a carbonyl group. Further, patent document 3 proposes: an oxime ester compound having a diphenyl sulfide skeleton or a carbazole skeleton and having a specific substituent containing a cycloalkyl group in an oxime ester group.

Documents of the prior art

Patent document

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 specification

Disclosure of Invention

Problems to be solved by the invention

However, conventional colored resin compositions using an oxime ester photoinitiator tend to have insufficient brightness. In particular, conventional high-sensitivity oxime ester photoinitiators tend to have a tendency to have a low luminance. On the other hand, an oxime ester photoinitiator which is relatively likely to exhibit good brightness has a low sensitivity, and the influence of the oxime ester photoinitiator on the sensitivity and brightness is in a trade-off relationship. Therefore, a colored resin composition which can realize high sensitivity and can form a colored layer having higher brightness is required.

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

Means for solving the problems

The photosensitive coloring resin composition for the color filter comprises: a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,

the photoinitiator contains an oxime ester compound represented by the following general formula (1):

[ chemical formula 1]

General formula (1)

(in the general formula (1), R^aAnd R^bAre each independently a hydrogen atom or an alkyl group; r^cIs a hydrocarbon group optionally containing at least 1-valent linking group selected from the group consisting of a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-); z is a hydrogen atom or- (C ═ O) R^d，R^dIs a hydrocarbon group optionally containing at least 1 selected from an oxygen atom and a sulfur atom, or a heterocyclic group containing no nitrogen atom and containing at least 1 selected from an oxygen atom and a sulfur atom; r^eIs a hydrocarbon group having 1 to 10 carbon atoms. )

The color filter of the present invention comprises at least a substrate and a colored layer provided on the substrate, wherein at least 1 of the colored layers is a colored layer comprising a cured product of the photosensitive colored resin composition for a color filter of the present invention.

In addition, the present invention provides a display device having the color filter of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a photosensitive colored resin composition for a color filter which can form a colored layer with improved brightness and has excellent sensitivity, a color filter having a colored layer formed by using the photosensitive colored resin composition for a color filter, and a display device using the color filter.

Drawings

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

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

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

Detailed Description

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

Note that, in the present invention, light includes electromagnetic waves of wavelengths in visible and non-visible regions, and also includes radiation including, for example, microwaves and electron beams. Specifically, the term "electromagnetic wave" means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

In the present invention, the term (meth) acrylic acid means acrylic acid and methacrylic acid; the term (meth) acrylate refers to both acrylates and methacrylates.

In the present specification, the chromaticity coordinates x and y are, unless otherwise specified, chromaticity coordinates in the XYZ color system of JIS Z8701 where color measurement is performed using a C light source.

I. Photosensitive coloring resin composition for color filter

[ chemical formula 2]

General formula (1)

The photosensitive coloring resin composition for the color filter of the invention can form a coloring layer with improved brightness and has good sensitivity by using the oxime ester compound shown in the general formula (1) as a photoinitiator. In addition, the photosensitive coloring resin composition for the color filter has the advantages of inhibiting the generation of development residues, and easily forming required micropores on a coloring layer when the coloring layer is patterned.

The effect of the above-described effect exerted by the photosensitive colored resin composition for color filters of the present invention using the oxime ester compound represented by the above general formula (1) as a photoinitiator is not clear, but is presumed as follows.

The luminance of the colored layer is reduced, and sometimes the coloring due to the reaction residue of the photoinitiator is one of the causes. It is presumed that the oxime ester initiator having high sensitivity but insufficient brightness of the colored layer has a structure in which the reaction residue of the photoinitiator is easily colored, for example, a carbazole skeleton. On the other hand, it is considered that the oxime ester compound represented by the general formula (1) used in the present invention has a structure which is less likely to cause coloring of the reactive residue and has high transmittance, and therefore coloring of the colored layer by the reactive residue is suppressed, and as a result, a colored layer having improved luminance can be formed.

Further, it is presumed that the oxime ester compound represented by the above general formula (1) used in the present invention has a fluorene skeleton and an oxime ester group via a carbonyl group, and therefore, the conjugated system of the structure does not adversely affect the luminance, and the sensitivity is improved by the structure which improves the absorption intensity at the time of exposure. Further, it is considered that 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, and has excellent sensitivity because radical migration occurs more rapidly than in a photopolymerization initiator which generates an alkyl radical or an aryl radical having a large number of carbon atoms.

Further, it is presumed that the oxime ester compound represented by the general formula (1) or the reactive residue thereof in the photosensitive colored resin composition for color filters of the present invention is likely to have high affinity for an aqueous alkali solution during alkali development, and therefore development residue is likely to be suppressed.

In addition, when the photosensitive coloring resin composition for the color filter is used for patterning a coloring layer, required micropores can be easily formed on the coloring layer. When a photoinitiator with higher sensitivity is used for forming a colored layer, radicals move to an unexposed portion after the radicals are generated, and the inside of an exposed portion retains the shape of a certain unexposed portion, and the peripheral portion of the unexposed portion is difficult to be in a non-jagged state. Therefore, in the case of a conventional photosensitive resin composition, when a highly sensitive photoinitiator capable of forming a fine line pattern is used, it is difficult to form micropores even if the linearity of the fine line pattern is good. As shown in comparative example 2 described later, when a photoinitiator having relatively low sensitivity is used, the residual film ratio is lowered even if micropores can be formed. In contrast, the photosensitive colored resin composition for color filters of the present invention can easily form micropores by using the oxime ester compound represented by the general formula (1). In particular, by adjusting the content of the photoinitiator and the content of the antioxidant used in combination, fine-shaped micropores can be formed more easily. The photosensitive colored resin composition for color filters of the present invention is easy to form desired fine holes in a colored layer, and therefore, is also suitable for use in applications where, for example, a colored layer is formed on a TFT (Thin Film Transistor) substrate for forming a reflective color filter and a through hole for conduction is formed in the colored layer.

Further, since the oxime ester compound represented by the general formula (1) used in the present invention has an oxime ester group via a carbonyl group in a fluorene skeleton, the crystallinity is reduced as compared with an oxime ester compound having a structure in which an oxime ester group is not bonded to a fluorene skeleton via a carbonyl group, and therefore, the solvent solubility and the solvent resolubility are improved, and the compatibility with other components is improved. By using a photoinitiator having improved solvent solubility, solvent re-solubility, and compatibility with other components, the linearity of the fine line pattern is improved, or the jaggy of the fine hole is easily suppressed.

Further, since the oxime ester compound represented by the above general formula (1) has a high thermal decomposition temperature, the generation of outgas during heating of a coating film can be suppressed. Therefore, the resist has high reliability, and when another layer such as a conductive film is further stacked on the coating film, for example, damage to the stacked layer due to outgassing can be suppressed.

The photosensitive coloring resin composition for the color filter comprises: the color material, the alkali-soluble resin, the photopolymerizable compound, the photoinitiator, and the solvent may further contain other components within a range not impairing the effects of the present invention.

The components of the colored resin composition of the present invention will be described in detail below in order from the photoinitiator according to the characteristics of the present invention.

[ photoinitiator ]

< Oxime ester Compound represented by the general formula (1) >

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

In the above general formula (1), R^aAnd R^bEach independently is a hydrogen atom or an alkyl group. From the viewpoint of solvent solubility and compatibility with other components, R^aAnd R^bPreferably each independently is an alkyl group. The alkyl group may be any of linear, branched, cyclic, or a combination thereof. Examples of the alkyl group include: 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, methylcyclopentyl group, cyclopentylmethyl group, cyclohexyl group, etc., and among them, an alkyl group having 2 to 6 carbon atoms is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and a linear alkyl group having 2 to 4 carbon atoms is particularly preferable.

In the above general formula (1), R^cIs a hydrocarbyl group optionally comprising at least 1 divalent linking group selected from thioether linkage (-S-), ether linkage (-O-), and carbonyl linkage (-CO-).

As the above-mentioned R^cExamples of the hydrocarbon group of (1) include: alkyl, alkenyl, aryl, aralkyl, and the like. The alkyl group may be linear, branched or cyclic, or may be a combination of linear and cyclic. Examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylethyl, bornyl, isobornyl, dicyclopentyl, adamantyl, lower alkyl-substituted adamantyl, and the like. The alkenyl group may be linear, branched or cyclic, and examples thereof include: vinyl, allyl, propenyl, and the like. Examples of the aryl group include: phenyl, biphenyl, naphthyl, tolyl, xylyl, and the like. Examples of the aralkyl group include: benzyl, phenethyl, naphthylmethyl, naphthylethyl and the like. As R^cThe hydrocarbon group of (1) 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 or an aryl group having 6 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms. In addition, when the micropores are formed in the colored layer, R is from the viewpoint of improving the shape of the micropores^cThe number of carbon atoms of the hydrocarbon group (2) or more is preferable. In addition, from the viewpoint of solvent solubility and compatibility, R is^cThe hydrocarbon group (b) is preferably a structure containing a cyclic or linear alkyl group such as a cyclopentylmethyl group or a cyclohexylmethyl group.

In addition, the above R^cIn the present invention, the hydrocarbon group containing the 2-valent linking group can improve the solubility in a solvent and the compatibility. The 2-valent linking group is preferably a thioether bond (-S-), or an ether bond (-O-) from the viewpoint of improving the solubility in a solvent. R is as defined above^cIn the case where the hydrocarbon group contains the 2-valent linking group, the hydrocarbon group may be bonded to a carbon atom of the oxime ester group via the 2-valent linking group, or a carbon atom of the hydrocarbon group may be directly bonded to a carbon atom of the oxime ester group. R is as defined above^cIn the case where the hydrocarbon group contains the above-mentioned 2-valent linking group and the carbon atom of the hydrocarbon group is directly bonded to the carbon atom of the oxime ester group, examples thereof include the above-mentioned R^cThis is the case of a group in which hydrocarbon groups are bonded to each other by the above-mentioned 2-valent linking group. Examples of the group in which hydrocarbon groups are bonded to each other by the above-mentioned 2-valent linking group include: a structure containing a thioether bond (-S-) such as an alkylthioalkyl group such as a methylthiomethyl group, or an arylthioalkyl group; ether bond (-O-) containing structures such as methoxymethyl, methoxycyclohexyl, alkoxyalkyl, and aryloxyalkyl; structures containing a carbonyl bond (-CO-), such as an acetylmethyl group, a benzoylmethyl group, and an acylalkyl group.

In the above general formula (1), Z is a hydrogen atom or- (C ═ O) R^d，R^dIs a hydrocarbon group optionally containing at least 1 selected from an oxygen atom and a sulfur atom, or a nitrogen atom-free hydrocarbon group containing at least one selected from an oxygen atom and a sulfur atom1 kind of heterocyclic radical is less.

As the above-mentioned R^dThe hydrocarbon group optionally containing at least 1 selected from an oxygen atom and a sulfur atom in (b) may be exemplified by: is further selected from the above R^cThe hydrocarbon group as described above, the above R^cThe hydrocarbon group includes at least 1 kind of connecting group of oxygen atom such as ether bond (-O-), carbonyl bond (-CO-) and the like, and sulfur atom containing connecting group such as thioether bond (-S-), wherein the hydrocarbon group is 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, and further preferably an aryl group having 6 to 10 carbon atoms.

In addition, as the heterocyclic ring in the heterocyclic group containing no nitrogen atom but containing at least 1 kind selected from an oxygen atom and a sulfur atom, for example: furan rings, benzofuran rings, thiophene rings, benzothiophene rings, thienothiophene rings, furofuran rings, thienofuran rings, and the like. R is as defined above^dThe hydrocarbon group or the heterocyclic group of (2) is preferably one having 1 to 10 carbon atoms from the viewpoint of developability.

Among the above Z, a hydrogen atom is preferable from the viewpoint of developability and brightness. On the other hand, when Z is- (C ═ O) R^dThe solubility and compatibility of the solvent can be improved.

In the above general formula (1), R^eIs a hydrocarbon group having 1 to 10 carbon atoms. Examples of the C1-10 hydrocarbon group include the above-mentioned R^cThe hydrocarbon group has 1 to 10 carbon atoms. Wherein, from the viewpoint of improving sensitivity, the above R^ePreferably 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, still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

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

Examples of the oxime ester compound represented by the general formula (1) include: r is^aAnd R^bAlkyl and R both having 1 to 4 carbon atoms^cIs C1-4 alkyl, Z is hydrogen atom, R^eA compound which is an alkyl group having 1 to 4 carbon atoms; r^aAnd R^bAlkyl group and R both having 1 to 6 carbon atoms^cAn alkyl group having 4 to 10 carbon atoms, Z being a combination of a linear alkyl group and a cyclic alkyl group, R being a hydrogen atom^eA compound which is an alkyl group having 1 to 4 carbon atoms; r is^aAnd R^bAll are hydrogen atom or C1-C4 alkyl, R^cIs C1-4 alkyl, Z is- (C ═ O) R^d、R^dAryl with 6-10 carbon atoms, R^eExamples of suitable compounds include, but are not limited to, compounds containing an alkyl group having 1 to 4 carbon atoms.

The oxime ester compound represented by the general formula (1) includes, for example, at least 1 selected from the following compounds (1-1) to (1-4) as a more suitable compound.

[ chemical formula 3]

Compound (1-1)

Compound (1-2)

Compound (1-3)

Compound (1-4)

The oxime ester compound represented by the general formula (1) can be synthesized by, for example, using fluorene or a derivative thereof in place of diphenyl sulfide or a derivative thereof and appropriately selecting a solvent, a reaction temperature, a reaction time, a purification method, and the like according to the materials to be used, with reference to Japanese patent laid-open No. 2012-526185.

In the colored resin composition of the present invention, the photoinitiator preferably contains 2 or more kinds of oxime ester compounds having no carbazole skeleton, from the viewpoint of forming a colored layer having improved brightness, having good sensitivity, and facilitating adjustment of line width in pattern formation. Since the reaction residue of the oxime ester compound having no carbazole skeleton is less likely to cause coloring, a decrease in luminance of the colored layer can be suppressed. Further, by appropriately selecting and combining 2 or more kinds of oxime ester compounds containing an 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 2 or more kinds of oxime ester compounds having no carbazole skeleton, the colored resin composition may contain at least 1 or more kinds of oxime ester compounds represented by the above general formula (1), may contain 2 or more kinds of oxime ester compounds represented by the above general formula (1), or may contain an oxime ester compound represented by the above general formula (1) and an oxime ester compound having no carbazole skeleton other than the oxime ester compound represented by the above general formula (1) in combination.

Among them, from the viewpoint of not significantly reducing the brightness, developability and sensitivity and easily improving the shape of micropores, it is preferable to use an oxime ester compound represented by the above general formula (1) in combination with an oxime ester compound having a diphenyl sulfide skeleton.

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 suitably used.

[ chemical formula 4]

General formula (2)

(in the general formula (2), R^c’And R^fEach independently is a C1-14 hydrocarbon group optionally containing at least 1 2-valent connecting group selected from thioether bond (-S-), ether bond (-O-) and carbonyl bond (-CO-); z¹Is hydrogen atom, nitro or- (C ═ O) R^d’，R^d’Is a hydrocarbon group optionally containing at least 1 selected from oxygen atoms and sulfur atoms, or contains no nitrogen atom but contains oxygen selected from oxygen atomsA heterocyclic group of at least 1 of an atom and a sulfur atom. )

As R in the above general formula (2)^c’And R^fThe hydrocarbon group having 1 to 14 carbon atoms optionally containing at least 1 2-valent linking group selected from the group consisting of a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-), and examples thereof include R in the general formula (1)^cThe (b) optionally contains at least 1 of 2-valent linking groups selected from thioether bond (-S-), ether bond (-O-) and carbonyl bond (-CO-), and the hydrocarbon groups with the same carbon number from 1 to 14 are selected. R as the above general formula (2)^c’As R of the above general formula (1), those which are also preferably used^cBut the groups used are preferred. R as the above general formula (2)^fParticularly, from the viewpoint of improving sensitivity, an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms are preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is even more preferable, and a methyl group is particularly preferable.

Z in the above general formula (2)¹Is hydrogen atom, nitro or- (C ═ O) R^d’，R^d’Is a hydrocarbon group optionally containing at least 1 selected from an oxygen atom and a sulfur atom, or a heterocyclic group containing no nitrogen atom but containing at least 1 selected from an oxygen atom and a sulfur atom; as the R^d’Examples thereof include R of the above general formula (1)^dThe same groups. Z above¹Of these, hydrogen atom or- (C ═ O) R is preferable from the viewpoints of developability and luminance in particular^d’From the viewpoint of brightness, a hydrogen atom is more preferable.

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

Examples of the oxime ester compound represented by the general formula (2) include: r^c’An alkyl group having 6 to 10 carbon atoms, Z, wherein the alkyl group is a combination of a linear alkyl group and a cyclic alkyl group¹Is a hydrogen atom, R^fA compound which is an alkyl group having 1 to 4 carbon atoms; r^c’An alkyl group having 6 to 10 carbon atoms, Z, wherein the alkyl group is a combination of a linear alkyl group and a cyclic alkyl group¹Is- (C ═ O) R^d’R is a hydrogen atom^d’Is free of nitrogen atoms but containing sulfur atomsHeterocyclic group of (A), R^fAnd compounds having an alkyl group having 1 to 4 carbon atoms, but the present invention is not limited thereto.

The oxime ester compound represented by the general formula (2) includes, for example, at least 1 selected from the following compounds (2-1) to (2-2) as a more suitable compound.

[ chemical formula 5]

Compound (2-1)

Compound (2-2)

The oxime ester compound represented by the general formula (2) can be synthesized, for example, by referring to Japanese patent laid-open publication No. 2012-526185.

The photosensitive colored resin composition for color filters of the present invention may further contain a photoinitiator other than the oxime ester compound. The photoinitiator used in the colored resin composition of the present invention may contain a chain transfer agent in addition to the photopolymerization initiator.

< other photoinitiators >

Examples of other photoinitiators include: oxime ester photoinitiators other than the oxime ester compound having no carbazole skeleton, which contains the oxime ester compound represented by the general formula (1), α -amino ketone photoinitiators, diimidazole (biimidazole) photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, mercapto chain transfer agents, and the like.

Among them, from the viewpoint of further improving the linearity in forming a fine line pattern while further improving the brightness, or improving the ability to form a fine line pattern designed such as the mask line width, and from the viewpoint of improving the shape of micropores, it is preferable to further use at least 1 selected from the group consisting of an α -amino ketone photoinitiator, a diazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent in combination with the oxime ester compound represented by the general formula (1). Among these, it is preferable to use an acylphosphine oxide photoinitiator in combination, from the viewpoint of suppressing jaggies at the end of the pore and facilitating formation of fine pores with good dimensional accuracy when forming fine pores. It is considered that the acylphosphine oxide-based photoinitiator has a higher thermal decomposition temperature than other initiators, and therefore, is less likely to cause side reactions by heating during prebaking, and thus, jaggy is suppressed.

The term "linearity improvement" means that the end of the colored layer formed in the developing step after the application of the coloring composition has few irregularities and is formed linearly or almost linearly. The term "jaggy" means that the pattern ends are not uniform in straight lines or curved lines, and dimensional accuracy is deteriorated.

From the viewpoint of improving the shape of micropores and suppressing jaggies, at least 1 selected from the group consisting of an α -aminoketone photoinitiator, a diazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent is preferably used in combination with the oxime ester compound having a diphenyl sulfide skeleton, and more preferably, the antioxidant described later is used in combination with the oxime ester compound.

The α -aminoketone photoinitiator has a property of causing intermediate curing from the surface of the coating film, and easily suppressing the curing in the deep part of the coating film, and therefore, when combined with the oxime ester compound represented by the general formula (1), the α -aminoketone photoinitiator tends to improve the curing in the deep part of the coating film, which is preferable.

Examples of the α -aminoketone photoinitiator include: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (e.g., IRGACURE 907, BASF), 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (e.g., IRGACURE369, BASF), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (IRGACURE 379EG, BASF) and the like.

The α -aminoketone photoinitiator may be used singly or in combination of 2 or more, and among them, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone are preferable from the viewpoint of increasing the residual film rate; from the viewpoint of suppressing jagging of micropores, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is more preferable.

The imidazole-based photoinitiator has a property of curing a deep portion of a coating film, and is preferable in that curability of the surface of the coating film is easily suppressed, and when combined with the oxime ester compound represented by the general formula (1), curability of the surface of the coating film tends to be improved.

Examples of the diimidazole-based photoinitiator include: 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (4-ethoxycarbonylphenyl) -1, 2 ' -diimidazole, 2 ' -bis (2-bromophenyl) -4, 4 ', 5, 5 ' -tetrakis (4-ethoxycarbonylphenyl) -1, 2 ' -diimidazole, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetraphenyl-1, 2 ' -diimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4, 4 ', 5, 5 ' -tetraphenyl-1, 2 ' -diimidazole, 2 ' -bis (2, 4, 6-trichlorophenyl) -4, 4 ', 5, 5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2-bromophenyl) -4, 4 ', 5, 5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2, 4-dibromophenyl) -4, 4 ', 5, 5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2, 4, 6-tribromophenyl) -4, 4 ', 5, 5 ' -tetraphenyl-1, 2 ' -biimidazole, and the like.

The diimidazole-based photoinitiator may be used singly or in combination of 2 or more, and among them, it is preferably used in combination with a mercapto-based chain transfer agent from the viewpoint of improving curability of a coating film.

Examples of the thioxanthone photoinitiator include: 2, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2, 4-dichlorothioxanthone, and the like.

The thioxanthone photoinitiator may be used singly or in combination of 2 or more, and among them, 2, 4-isopropylthioxanthone and 2, 4-diethylthioxanthone are preferably used from the viewpoint of improving the transfer of radical generation.

The acylphosphine oxide photoinitiator is suitable for improving the brightness because it has a property of causing little yellowing by heat, but generally has low sensitivity and cannot obtain sufficient curability in some cases. However, it is preferable to combine the oxime ester compound represented by the general formula (1) with the oxime ester compound because the curability of the entire coating film is improved, and when micropores are formed, jaggies at the end portions of the pores are suppressed, and thus micropores with good dimensional accuracy are easily formed.

Examples of the acylphosphine oxide photoinitiator include: benzoyl-diphenylphosphine oxide, 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2, 3, 5, 6-tetramethylbenzoyl-diphenylphosphine oxide, 3, 4-dimethylbenzoyl-diphenylphosphine oxide, 2, 4, 6-trimethylbenzoyl-phenylethoxyphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4, 4-trimethyl-pentylphosphine oxide, bis (2, 6-dimethylbenzoyl) -ethylphosphine oxide, and the like.

The acylphosphine oxide photoinitiator may be used singly or in combination of 2 or more, and bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide is preferably used from the viewpoint of improving the curability of the coating film.

The mercapto group-based chain transfer agent has a property of receiving a radical from a radical which is relatively slow in reaction to accelerate the reaction, and in particular, it is preferable to use a combination of a diimidazole-based photoinitiator from the viewpoint of a high tendency to increase the reaction speed.

Examples of the mercapto chain transfer agent include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1, 4-bis (3-mercaptobutanoyloxy) butane, 1, 3, 5-tris (3-mercaptobutoxyethyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), and the like .

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

The total content of the photoinitiators used in the photosensitive colored resin composition for color filters of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and is preferably in the range of 0.1 mass% or more and 12.0 mass% or less, more preferably 1.0 mass% or more and 8.0 mass% or less, relative to the total solid content of the photosensitive colored resin composition for color filters. If the content is not less than the lower limit, the photocuring is sufficiently promoted to suppress elution of the exposed portion during development, while if the content is not more than the upper limit, the yellowing of the obtained colored layer can be suppressed from increasing and the luminance can be suppressed from decreasing.

The term "solid" means all components other than the solvent, and includes liquid polyfunctional monomers and the like.

The content of the oxime ester compound represented by the general formula (1) used in the photosensitive colored resin composition for color filters of the present invention is preferably in the range of 0.1 mass% to 8.0 mass%, more preferably 0.5 mass% to 6.0 mass%, based on the total solid content of the photosensitive colored resin composition for color filters. If the content is not less than the lower limit, the photocuring is sufficiently promoted to suppress elution of the exposed portion during development, while if the content is not more than the upper limit, the yellowing of the obtained colored layer is suppressed from being enhanced and the luminance is suppressed from being lowered.

When the photoinitiator of the photosensitive colored resin composition for color filters of the present invention contains 2 or more kinds of oxime ester compounds having no carbazole skeleton, the total content of the 2 or more kinds of oxime ester compounds having no carbazole skeleton including the oxime ester compound represented by the general formula (1) is preferably in the range of 0.1 mass% or more and 12.0 mass% or less, more preferably 1.0 mass% or more and 8.0 mass% or less, relative to the total solid content of the photosensitive colored resin composition for color filters, from the viewpoint of sufficiently exerting the effect of being used in combination with the photoinitiator.

In the case where the oxime ester compound having a diphenyl sulfide skeleton is combined with the oxime ester compound represented by the general formula (1), the photoinitiator used in the present invention is preferably contained in an amount of 0.1 to 4.0 mass%, more preferably in an amount of 0.3 to 3.0 mass%, based on the total solid content of the photosensitive colored resin composition for color filters, from the viewpoint of sufficiently exhibiting the effect of combining the oxime ester compound represented by the general formula (1) with the oxime ester compound having a diphenyl sulfide skeleton.

When the oxime ester compound having a diphenyl sulfide skeleton is combined with the oxime ester compound represented by the general formula (1) as the photoinitiator used in the present invention, the ratio of the oxime ester compound represented by the general formula (1) to the oxime ester compound having a diphenyl sulfide skeleton 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 with respect to 100 parts by mass of the oxime ester compound represented by the general formula (1) from the viewpoints of brightness and sensitivity. From the viewpoint of easy formation of micropores, the oxime ester compound having a diphenyl sulfide skeleton is preferably 10 parts by mass or more and 70 parts by mass or less, more preferably 15 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the oxime ester compound represented by the general formula (1).

In addition, when the photoinitiator of the photosensitive colored resin composition for color filters of the present invention further includes a photoinitiator other than the above, the total content of the oxime ester compound represented by the general formula (1) and 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, and still more preferably 50 parts by mass or more, per 100 parts by mass of the total of the photoinitiators used in the present invention.

On the other hand, from the viewpoint of sufficiently exerting the effect of being used in combination with the other photoinitiator, the total content of the oxime ester compound represented by the general formula (1) and the oxime ester compound having a diphenyl sulfide skeleton is preferably 95 parts by mass or less, more preferably 85 parts by mass or less, based on 100 parts by mass of the total of the photoinitiators used in the present invention.

When the photoinitiator used in the present invention further contains at least 1 selected from the group consisting of an α -amino ketone photoinitiator, a diazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent, the total content thereof is preferably in the range of 0.1 mass% or more and 4.0 mass% or less, more preferably 0.5 mass% or more and 2.0 mass% or less, relative to the total solid content of the photosensitive colored resin composition for color filters, from the viewpoint of sufficiently exerting the effect of combining these photoinitiators.

[ color material ]

In the present invention, the color material is not particularly limited as long as it can develop a desired color when forming a colored layer of a color filter, and 2 or more kinds of various organic pigments, inorganic pigments, dispersible dyes, and dyes can be used alone or in combination. Among these, organic pigments are preferable because they have high color developability and high heat resistance. As The organic Pigment, there may be mentioned compounds classified as pigments (pigments) in The color index (C.I.; published by The Society of Dyers and Colourists Co., Ltd.), specifically, compounds to which The color index (C.I.) number as described below is assigned.

In the following description, when only the numbers of the listed color index names are different, only the numbers may be listed.

C.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185;

c.i.

pigment orange

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

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38;

c.i.

pigment red

1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57:1, 57:2, 58:4, 60:1, 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, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 255, 202, 209, 215, 220, 265;

c.i. pigment blue 15, 15:3, 15:4, 15:6, 60;

c.i. pigment green 7, 36, 58, 59;

c.i. pigment brown 23, 25;

c.i. pigment black 1, 7.

Specific examples of the inorganic pigment include: titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, prussian blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, and the like.

For example, when a light-shielding layer pattern is formed on a substrate of a color filter using the photosensitive colored resin composition for a color filter of the present invention, a black pigment having high light-shielding property is blended in the ink. As the black pigment having high light-shielding property, for example: inorganic pigments such as carbon black and ferroferric oxide, and organic pigments such as cyanine black.

Examples of the dispersible dye include: a lake material which is a dispersible dye obtained by imparting various substituents to a dye and making the dye insoluble in a solvent, a dispersible dye obtained by using a solvent having low solubility in combination, or a insolubilized (laked) dye obtained by forming a salt of a dye soluble in a solvent and a counter ion. By using such a dispersible dye in combination with a dispersant, the dispersibility and dispersion stability of the dye can be improved.

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

The dye may be appropriately selected from conventionally known dyes. Examples of such dyes include: azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, and the like. Specifically, examples thereof include: c.i. solvent yellow 4, 14, 15, 24, 82, 88, 94, 98, 162, 179;

c.i. solvent red 45, 49;

c.i. solvent orange 2, 7, 11, 15, 26, 56;

c.i. solvent blue 35, 37, 59, 67;

c.i. acid red 50, 52, 289;

c.i. acid violet 9, 30;

c.i. acid blue 19, and the like.

In forming the blue colored layer, at least 1 of triarylmethane dyes, xanthene dyes and cyanine dyes is particularly preferable from the viewpoint of high brightness, and at least 1 selected from triarylmethane dyes and xanthene dyes is preferable from the viewpoint of high heat resistance.

In the present invention, from the viewpoint of enhancing the luminance of the color filter, the lake material containing a triarylmethane-based dye is preferably contained, and more preferably contains a triarylmethane-based basic dye and a polyacid anion.

In the present invention, the lake color material is particularly preferably a color material represented by the following general formula (i) which forms a molecular association state and is more preferable in terms of exhibiting more excellent heat resistance, from the viewpoints of excellent heat resistance and light resistance and achieving higher luminance of a color filter.

[ chemical formula 6]

General formula (i)

(in the general formula (I), A is an a-valent organic compound having no pi bond with a carbon atom directly bonded to NThe organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N or an aromatic group having the aliphatic hydrocarbon group, and O, S, N may be contained in the carbon chain. B is^c-Represents a polyoxometalate anion (polyoxometalate anion). Rⁱ～R^vEach independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, RⁱⁱAnd Rⁱⁱⁱ、R^ivAnd R^vOr may be bonded to form a ring structure. Ar (Ar)¹Represents a 2-valent aromatic group optionally having a substituent. Plural Rⁱ～R^vAnd Ar¹May be the same or different, respectively;

a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. e is 0 or 1, and a bond is absent when e is 0. The plurality of e 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.

In the general formula (i), a is an a-valent organic group having no pi bond to a carbon atom directly bonded to N (nitrogen atom), the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain may contain O (oxygen atom), S (sulfur atom), and N (nitrogen atom). Since the carbon atom directly bonded to N does not have a pi bond, the color characteristics such as hue and transmittance of the cationic color-developing site are not affected by the linking group a and other color-developing sites, and the same color as that of the monomer can be maintained.

In a, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be any of linear, branched or cyclic as long as the terminal carbon atom directly bonded to N does not have a pi bond, and the carbon atom other than the terminal may have an unsaturated bond or a substituent, and may contain O, S, N in the carbon chain. For example, it may contain a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, etc., and a hydrogen atom may be further substituted with a halogen atom, etc.

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

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

Among the cyclic aliphatic hydrocarbon groups, a bridged alicyclic hydrocarbon group is preferable from the viewpoint of the robustness of the skeleton. The bridge-containing alicyclic hydrocarbon group is a polycyclic aliphatic hydrocarbon group having a bridged structure and a polycyclic structure within the aliphatic ring, and examples thereof include: norbornane, bicyclo [2, 2, 2] octane, dicyclopentadiene, adamantane, and the like. Among the bridged alicyclic hydrocarbon groups, norbornane is preferred. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring, and among them, a group containing a benzene ring is preferable.

From the viewpoint of ease of raw material acquisition, a is preferably 2 or more and 4 or less, preferably 2 or more and 3 or less, and more preferably 2. For example, when a is a 2-valent organic group, there may be mentioned an aromatic group obtained by 2-substituted linear, branched or cyclic alkylene groups having 1 to 20 carbon atoms, and alkylene groups having 1 to 20 carbon atoms such as xylylene group.

Rⁱ～R^vThe alkyl group in (1) is not particularly limited. Examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, and among them, linear or branched alkyl groups having 1 to 8 carbon atoms are preferable, and linear or branched alkyl groups having 1 to 5 carbon atoms are more preferable from the viewpoint of easiness of production and supply of raw materials. Wherein R isⁱ～R^vThe alkyl group in (1) is particularly preferably an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include: aryl group, halogen atom, hydroxyl group and the like, and examples of the substituted alkyl group include benzyl group and the like.

Rⁱ～R^vAryl in (A) is not specifiedOtherwise defining. Examples thereof include phenyl and naphthyl. Examples of the substituent which the aryl group may have include an alkyl group and a halogen atom.

So-called RⁱⁱAnd Rⁱⁱⁱ、R^ivAnd R^vBonded to form a ring structure, means RⁱⁱAnd Rⁱⁱⁱ、R^ivAnd R^vA ring structure is formed via the nitrogen atom. The ring structure is not particularly limited, and examples thereof include: pyrrolidine ring, piperidine ring, morpholine ring, and the like.

Among them, from the viewpoint of chemical stability, preferred are: r isⁱ～R^vEach independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or RⁱⁱAnd Rⁱⁱⁱ、R^ivAnd R^vBond to form pyrrolidine ring, piperidine ring, morpholine ring.

Rⁱ～R^vThe above structures may be independently adopted, respectively, wherein R is preferable from the viewpoint of color purityⁱR is more preferably a hydrogen atom, and further from the viewpoint of easiness of production and raw material supplyⁱⁱ～R^vAre all the same.

Ar¹The 2-valent aromatic group in (1) is not particularly limited. The aromatic group may be a heterocyclic group, in addition to the aromatic hydrocarbon group including the carbocyclic ring. As the aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to the benzene ring, there can be mentioned: condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetrahydronaphthalene ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring; and chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, N in the chain skeleton, such as diphenyl ether. On the other hand, as the heterocyclic ring in the heterocyclic group, there can be mentioned: 5-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine and pyrazine; condensed polycyclic heterocycles such as benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline, and the like. These aromatic groups may have a substituent.

Examples of the substituent that the aromatic group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, and the like.

Ar¹The aromatic group preferably has 6 to 20 carbon atoms, and more preferably contains a condensed polycyclic carbon ring having 10 to 14 carbon atoms. Among them, phenylene group or naphthylene group is more preferable from the viewpoint of simple structure and low cost of raw materials.

Multiple R present within 1 moleculeⁱ～R^vAnd Ar¹May be the same or different. In the presence of a plurality of Rⁱ～R^vAnd Ar¹In the case where the color developing sites are the same, since the color developing sites exhibit the same color, the same color as that of the monomer of the color developing sites can be reproduced, which is preferable from the viewpoint of color purity. On the other hand, in the reaction of Rⁱ～R^vAnd Ar¹In the case where at least 1 of them is provided with different substituents, the color obtained by mixing a plurality of monomers can be reproduced and adjusted to a desired color.

An anion (B) of the color material represented by the general formula (i)^c-) Is a polyacid anion with a valence of more than 2.

Among them, the polyacid anion is preferably a polyacid anion containing at least 1 of tungsten (W) and molybdenum (Mo) from the viewpoint of high luminance and excellent heat resistance and light resistance, and is more preferably a polyacid anion containing at least tungsten and may contain molybdenum from the viewpoint of heat resistance.

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

Polyacid anion (B)^c-) When 1 or more kinds of the above polyacidic acid anions are used alone or 2 or more kinds are used in combination, the molar ratio of tungsten to molybdenum in the total polyacidic acid anions is preferably within the above range.

The color material represented by the general formula (i) may be used within a range not impairing the effects of the present inventionFurther comprises double salts of other cations or anions. Specific examples of such cations include, among other basic dyes: organic compounds having a functional group capable of forming a salt with an anion, such as an amino group, a pyridyl group, or an imidazolyl group, or metal ions such as sodium ion, potassium ion, magnesium ion, calcium ion, copper ion, or iron ion. Specific examples of the anion include, in addition to acid dyes: and a halide ion such as a fluoride ion, a chloride ion, and a bromide ion, and an anion of an inorganic acid. Examples of the anion of the inorganic acid include: phosphate ion, sulfate ion, chromate ion, tungstate ion (WO)₄ ^2-) Molybdate ion (MoO)₄ ^2-) And anions of oxoacids, and the like.

The color material represented by the general formula (i) can be produced, for example, by referring to International publication No. 2012/144520.

In addition, when forming a green colored layer, a green color material obtained by further combining a yellow color material with c.i. pigment green 59(PG59) and c.i. pigment green 58(PG58) which are zinc phthalocyanine pigments can be preferably used.

As a yellow coloring material that can be used in combination with a zinc phthalocyanine pigment such as PG59 or PG58, a derivative pigment of c.i. pigment yellow 150 is particularly preferable. Specific examples of the pigment derivative of c.i. pigment yellow 150 include a metal complex of a mono-, di-, tri-and tetraanion of an azo compound represented by the following general formula (ii) or one of its tautomeric structures, which acts as a host for at least 1 guest compound, and metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn and Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La. Such a c.i. pigment yellow 150 derivative pigment is preferably used from the viewpoint of improvement in brightness.

[ chemical formula 7]

General formula (ii)

(in the above general formula (ii), R³¹Each independently is OH, NH₂NH-CN, acylamino, alkylamino, or arylamino; r is³²Each independently is-OH or-NH₂)

Among them, the yellow color material preferably contains at least 1 kind of anion selected from the group consisting of mono-, di-, tri-and tetraanions of the azo compound represented by the above general formula (ii) and the azo compound having a tautomeric structure, and at least 2 kinds of metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, from the viewpoints of improving brightness and improving contrast.

It is presumed that when 2 or more kinds of metal ions are contained, crystal growth of the color material is suppressed and the color material can be made fine, and further, when the color material is used in combination with a dispersant described later, the color material is made fine in a dispersion liquid of the color material, and a colored layer with improved contrast can be formed.

Examples of the acyl group in the acylamino group in the general formula (ii) include: alkylcarbonyl, phenylcarbonyl, alkylsulfonyl, phenylsulfonyl, carbamoyl optionally substituted with alkyl, phenyl or naphthyl, sulfamoyl optionally substituted with alkyl, phenyl or naphthyl, amidino (guanyl) optionally substituted with alkyl, phenyl or naphthyl, and the like. The carbon number of the alkyl group is preferably 1 to 6. In addition, the above alkyl groups may also be substituted with, for example: F. halogen such as Cl, Br, -OH, -CN, -NH₂And/or alkoxy having 1 to 6 carbon atoms. In addition, the above-mentioned phenyl and naphthyl groups may also be substituted by, for example: F. halogen such as Cl, Br, -OH, -CN, -NH₂、-NO₂And C1-C6 alkyl and/or C1-C6 alkoxy.

The alkyl group in the alkylamino group in the general formula (ii) preferably has 1 to 6 carbon atoms. The above alkyl groups may also be substituted, for example: F. halogen such as Cl, Br, -OH, -CN, -NH₂And/or alkoxy having 1 to 6 carbon atoms.

Examples of the aryl group in the arylamino group in the general formula (ii) include a phenyl group and a naphthyl group, and these aryl groups may be represented by, for example: F. halogen such as Cl or Br, -OH, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, -NH₂、-NO₂and-CN, etc.

A general formula (ii) aboveIn the azo compounds showing the azo compounds and their tautomeric structures, R is the number R from the viewpoint of hue³¹Preferably, each independently is-OH, -NH₂-NH-CN, or alkylamino, 2R³¹May be the same or different, respectively.

In the above general formula (ii), 2R's are present from the viewpoint of hue³¹More preferably, both are-OH, both are-NH-CN, or 1 is-OH and the other is-NH-CN, and still more preferably both are-OH.

In addition, in the azo compound represented by the above general formula (ii) and the azo compound having a tautomeric structure, R is R from the viewpoint of hue³²More preferably, both are-OH.

When at least 2 metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn are contained, among the at least 2 metals, at least 1 metal that becomes a cation having a valence of 2 or 3, preferably at least 1 metal selected from the group consisting of Ni, Cu, and Zn, and more preferably at least Ni is contained.

Further, it preferably contains Ni and at least 1 metal selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn, and further preferably contains Ni and at least 1 metal selected from the group consisting of Zn, Cu, Al, and Fe. Among them, Ni and Zn, or Ni and Cu are particularly preferable as the at least 2 metals, and Ni and Zn are particularly preferable from the viewpoint of affinity with the zinc phthalocyanine pigment.

When ions of at least 2 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 the at least 2 metals may be appropriately adjusted.

Among them, the content ratio of Ni and at least 1 metal further selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Cu, and Mn is preferably set to Ni: the other at least one metal is contained in a molar ratio of 97: 3 to 10: 90, more preferably 90: 10 to 10: 90.

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

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

When containing ions of at least 2 metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, the derivative pigment of c.i. pigment yellow 150 may also contain metal ions different from the ions of the above specific metals. For example, at least 1 metal ion selected from the group consisting of Li, Cs, Mg, Na, K, Ca, Sr, Ba, and La may be contained.

Examples of the c.i. pigment yellow 150 derivative pigment in which the pigment contains ions of at least 2 metals include: in the case where at least 2 kinds of metal ions are contained in a common crystal lattice, and in the case where crystals each containing 1 kind of metal ion are aggregated in other crystal lattices, the aggregation is caused. Among them, from the viewpoint of further improving the contrast, it is preferable that at least 2 kinds of metal ions are contained in a common crystal lattice. Whether the crystal contains at least 2 metal ions in a common crystal lattice or the crystal contains 1 metal ion in each of the other crystal lattices is agglomerated can be appropriately determined by an X-ray diffraction method, for example, refer to japanese patent application laid-open No. 2014-12838.

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

The color material used in the present invention can be produced by a known method such as recrystallization and solute solvent milling. Further, commercially available color materials may be used after being subjected to a micronization treatment.

The total content of the color materials is preferably 3 to 65 mass%, more preferably 4 to 60 mass%, based on the total solid content of the photosensitive colored resin composition for color filters. If the color filter is coated with the photosensitive colored resin composition to a predetermined thickness (usually 1.0 μm to 5.0 μm) at the lower limit or more, the color layer has a sufficient color density. In addition, if the upper limit value is less than the above, a colored layer having sufficient hardness and adhesion to a substrate while having excellent storage stability can be obtained. In particular, when a colored layer having a high color material concentration is formed, the total content of the color materials is preferably 15 to 65 mass%, more preferably 25 to 60 mass%, based on the total solid content of the photosensitive coloring resin composition for color filters.

[ alkali-soluble resin ]

The alkali-soluble resin of the present invention has an acidic group, and can be appropriately selected from resins that function as binder resins and are soluble in an alkali developing solution used for pattern formation.

In the present invention, the "alkali-soluble resin" is defined as having an acid value of 40mgKOH/g or more.

The alkali-soluble resin preferred in the present invention is a resin having an acidic group (usually a carboxyl group), and specific examples thereof include: acrylic resins such as acrylic copolymers having a carboxyl group and styrene-acrylic copolymers having a carboxyl group, epoxy (meth) acrylate resins having a carboxyl group, and the like. Among these, those having a carboxyl group in a side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain are particularly preferable. This is because the film strength of the cured film formed is improved by containing the photopolymerizable functional group. Further, 2 or more kinds of acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers and epoxy acrylate resins may be used in combination.

The acrylic resin such as an acrylic copolymer containing a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group is, for example, a (co) polymer obtained by (co) polymerizing a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, another copolymerizable monomer by a known method.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include: (meth) acrylic acid, vinyl benzoate, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. In addition, for example: addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, and omega-carboxy-polycaprolactone mono (meth) acrylate. Further, as the precursor of the carboxyl group, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride, or the like may be used. Among them, (meth) acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. It was found that the solvent resistance of the colored layer obtained by the alkali-soluble resin having a hydrocarbon ring as a bulky group, particularly the swelling of the colored layer was suppressed. Although the effect is not clear, it is presumed that the molecular motion in the colored layer is suppressed by the inclusion of a bulky hydrocarbon ring in the colored layer, and as a result, the strength of the coating film is improved and swelling by the solvent is suppressed.

Examples of such a hydrocarbon ring include an optionally substituted cyclic aliphatic hydrocarbon ring, an optionally substituted aromatic ring, and a combination thereof, and the hydrocarbon ring may have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group, or an amide group. In the case where the alicyclic ring is contained, the heat resistance and adhesion of the colored layer are improved, and the brightness of the obtained colored layer is also improved.

Specific examples of the hydrocarbon ring include: cyclopropane, cyclobutane, cycloPentane, cyclohexane, norbornane, tricyclo [5.2.1.0^2，6]Aliphatic hydrocarbon rings such as decane (dicyclopentane) and adamantane; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; a chain polycyclic ring such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene, and a cardo structure represented by the following chemical formula (A).

[ chemical formula 8]

Chemical formula (A)

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

[ chemical formula 9]

General formula (B)

(in the general formula (B), R^MIs an optionally substituted hydrocarbon ring. )

When the alkali-soluble resin has a maleimide structure represented by the above general formula (B), the hydrocarbon ring has a nitrogen atom, and therefore, the compatibility with an alkali dispersant of a polymer having a structural unit represented by the following general formula (I) is very good, and the development residue-suppressing effect is improved.

R as the above general formula (B)^MSpecific examples of the optionally substituted hydrocarbon ring of (b) include, for example, the same hydrocarbon rings as the specific examples of the hydrocarbon ring.

The hydrocarbon ring is preferably an aliphatic ring in order to improve the heat resistance and adhesion of the colored layer and to improve the brightness of the obtained colored layer.

In addition, from the viewpoint of improving the curability of the colored layer and improving the solvent resistance (NMP swelling inhibition), it is particularly preferable to include the cardo structure represented by the above chemical formula (a).

In the alkali-soluble resin used in the present invention, it is preferable to use the acrylic copolymer having a hydrocarbon ring structural unit in addition to the structural unit having a carboxyl group, from the viewpoint of easily adjusting the amount of each structural unit and easily improving the function of the structural unit by increasing the amount of the structural unit having a hydrocarbon ring.

The structural unit having a carboxyl group and the acrylic copolymer having a hydrocarbon ring can be prepared by using the above-mentioned ethylenically unsaturated monomer having a hydrocarbon ring as the "other copolymerizable monomer".

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring to be used in combination with the oxime ester compound represented by the above general formula (1) include: cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, and the like are preferable, and styrene is more preferable, from the viewpoint that the effect of maintaining the cross-sectional shape of the colored layer after development even in heat treatment is large.

In addition, from the viewpoint of the effect of suppressing the development residue, the ethylenically unsaturated monomer having a hydrocarbon ring is preferably the monomer having a maleimide structure and styrene, and more preferably styrene.

The alkali-soluble resin used in the present invention also preferably has an olefinic double bond in a side chain. When the resin composition has an ethylenic double bond, the alkali-soluble resins may form a crosslinking bond with each other, with the photopolymerizable compound, or the like in the curing step of the resin composition in the production of the color filter. When the oxime ester compound represented by the general formula (1) is used in combination with the oxime ester compound used in the present invention, the film strength of the cured film is further improved, and the development resistance is improved, and the thermal shrinkage of the cured film is suppressed, so that the cured film has excellent adhesion to a substrate.

The method for introducing an olefinic double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. Examples thereof include a method of introducing an olefinic double bond into a side chain by adding a compound having an epoxy group and an olefinic double bond in the molecule, for example, glycidyl (meth) acrylate, to a carboxyl group of an alkali-soluble resin; a method of introducing a structural unit having a hydroxyl group into the copolymer, in which a compound having an isocyanate group and an olefinic double bond in a molecule is added to introduce an olefinic double bond into a side chain.

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

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

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

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

When the ratio of the carboxyl group-containing ethylenically unsaturated monomer is not less than the lower limit, the solubility of the obtained coating film in an alkali developer is sufficient, and when the ratio of the carboxyl group-containing ethylenically unsaturated monomer is not more than the upper limit, the formed pattern tends not to be easily peeled off from the substrate or the film on the surface of the pattern tends to be rough when the pattern is developed with the alkali developer.

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

The preferable weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably 1,000 to 50,000, more preferably 3,000 to 20,000. When the weight average molecular weight is less than 1,000, the binder function after curing may be significantly reduced, and when the weight average molecular weight exceeds 50,000, pattern formation may be difficult when developing with an alkali developing solution.

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

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

The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride may be appropriately selected from known ones and used. The epoxy (meth) acrylate resin having a carboxyl group may be used alone in 1 kind or in combination with 2 or more kinds.

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

The acid value in the present invention can be measured in accordance with JIS K0070.

When the alkali-soluble resin has an ethylenically unsaturated group in a side chain thereof, the ethylenically unsaturated bond equivalent is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500, from the viewpoint of obtaining the effect of improving the film strength of the cured film, improving the development resistance, and excellent adhesion to the substrate by combining the oxime ester compound represented by the above general formula (1) used in the present invention. When the equivalent weight of the ethylenically unsaturated bond is 2000 or less, the developing resistance and the adhesion are excellent. Further, if the ratio is 100 or more, the ratio of the other structural units such as the structural unit having a carboxyl group and the structural unit having a hydrocarbon ring is relatively increased, and thus the developing property and the heat resistance are excellent. The oxime ester compound represented by the above general formula (1) used in the present invention is preferably used in combination with the above content.

Here, the "equivalent of the ethylenic unsaturated bond" means a weight average molecular weight of the ethylenic unsaturated bond per 1 mole in the alkali-soluble resin, and is represented by the following numerical formula (1):

digital type (1)

Equivalent of ethylenically unsaturated bond (g/mol) ═ W (g)/M (mol)

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

The above-mentioned ethylenically unsaturated bond equivalent can be obtained, for example, by the following method in accordance with JIS K0070: 1992, the number of olefinic double bonds contained in 1g of the alkali-soluble resin was measured and calculated.

The alkali-soluble resin used in the photosensitive coloring resin composition for color filters may be used alone in 1 kind, or may be used in combination in 2 or more kinds, and the content thereof is not particularly limited, but the alkali-soluble resin is preferably in the range of 5 to 60 mass%, more preferably 10 to 40 mass%, relative to the total solid content of the photosensitive coloring resin composition for color filters. When the alkali-soluble resin content is not less than the lower limit, sufficient alkali developability can be obtained, and when the alkali-soluble resin content is not more than the upper limit, film roughness and pattern defects can be suppressed during development.

[ photopolymerizable Compound ]

The photopolymerizable compound used in the photosensitive colored resin composition for color filters is not particularly limited as long as it is polymerizable by the photoinitiator, and a compound having 2 or more ethylenically unsaturated double bonds is usually suitably used, and a polyfunctional (meth) acrylate having 2 or more acryloyl groups or methacryloyl groups is particularly preferable.

Such a polyfunctional (meth) acrylate may be suitably selected from conventionally known polyfunctional (meth) acrylates and used. Specific examples thereof include those described in Japanese patent laid-open publication No. 2013-029832.

These polyfunctional (meth) acrylates may be used alone in 1 kind, or 2 or more kinds may be used in combination. When excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition for color filters of the present invention, the polyfunctional (meth) acrylate is preferably a poly (meth) acrylate of a polyhydric alcohol having 3 or more (trifunctional) polymerizable double bonds, preferably 3 or more members, or a dicarboxylic acid modified product thereof, and specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, a succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, a succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.

The content of the photopolymerizable compound used in the photosensitive colored resin composition for color filters is not particularly limited, but the photopolymerizable compound is preferably within a range of 5 to 60 mass%, more preferably 10 to 40 mass%, relative to the total solid content of the photosensitive colored resin composition for color filters. When the content of the photopolymerizable compound is not less than the lower limit, photocuring proceeds sufficiently and elution of the exposed portion during development can be suppressed, and when the content of the photopolymerizable compound is not more than the upper limit, alkali developability is sufficient.

The content of the photopolymerizable compound and the content of the photoinitiator used in the photosensitive colored resin composition for color filters are preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the photopolymerizable compound, from the viewpoint of excellent curability and residual film ratio, and from the viewpoint of improving electrical reliability.

[ solvent ]

The solvent used in the present invention is not particularly limited, and is not reactive with each component in the photosensitive colored resin composition for color filters, but may be an organic solvent capable of dissolving or dispersing the components. The solvent may be used alone or in combination of 2 or more.

Specific examples of the solvent include: alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, methyl alcohol, and ethyl alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; glycol ether acetate solvents such as ethyl methoxyacetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, and ethoxyethyl acetate; carbitol acetate-based solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and Butyl Carbitol Acetate (BCA); diacetates such as propylene glycol diacetate and 1, 3-butanediol diacetate; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; aprotic amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ -butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as n-heptane, n-hexane, and n-octane; and aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate based solvents, carbitol acetate based solvents, glycol ether based solvents, and ester based solvents can be suitably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention is preferably at least 1 selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Butyl Carbitol Acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate and 3-methoxybutyl acetate, from the viewpoint of solubility of other components and coatability.

In the photosensitive colored resin composition for a color filter of the present invention, the content of the solvent may be appropriately set within a range in which a colored layer can be formed with high accuracy. The content of the solvent is preferably in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass, based on the total amount of the photosensitive colored resin composition for color filters containing the solvent. When the solvent content is within the above range, a composition having excellent coatability can be obtained.

[ dispersing agent ]

In the photosensitive colored resin composition for color filters of the present invention, the color material is preferably dispersed in a solvent by a dispersant. In the present invention, the dispersant may be appropriately selected from conventionally known dispersants. As the dispersant, for example, a surfactant such as a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a silicone surfactant, and a fluorine surfactant can be used. Among the surfactants, a polymeric dispersant is preferable from the viewpoint of obtaining uniform and fine dispersion.

Examples of the polymeric dispersant include: (co) polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts, (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid; (Co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and modified products thereof; polyurethanes; unsaturated polyamides; polysiloxanes; long chain polyaminoamide phosphates; polyethyleneimine derivatives [ amides obtained by reaction of poly (lower alkyleneimine) with polyester containing free carboxyl group and their bases ]; polyallylamine derivatives (reaction products obtained by reacting polyallylamine with 1 or more compounds selected from 3 compounds selected from polyesters having free carboxyl groups, polyamides, and cocondensates of esters and amides (polyesteramides)), and the like.

The polymer dispersant is preferably a polymer dispersant having an amine value and containing a nitrogen atom in a main chain or a side chain, particularly from the viewpoint of being able to disperse the color material appropriately and having good dispersion stability, and is preferably a polymer dispersant composed of a polymer containing a repeating unit having a tertiary amine, particularly from the viewpoint of having good dispersibility, preventing the precipitation of foreign matter at the time of forming a coating film, and improving brightness and contrast.

The repeating unit having a tertiary amine is a site having affinity with the color material. A polymeric dispersant composed of a polymer containing a repeating unit having a tertiary amine generally contains a repeating unit serving as a site having affinity with a solvent. The polymer containing a repeating unit having a tertiary amine is particularly preferably a block copolymer having a block portion composed of a repeating unit containing a tertiary amine and a block portion having solvent affinity, from the viewpoint of excellent heat resistance and capability of forming a high-brightness coating film.

The repeating unit having a tertiary amine 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 these, preferred are repeating units having a tertiary amine in a side chain, and more preferred are those having a structure represented by the following general formula (I) in terms of being less likely to undergo thermal decomposition in the main chain skeleton and having high heat resistance:

[ chemical formula 10]

General formula (I)

(in the general formula (I), R¹Is a hydrogen atom or a methyl group, Q is a 2-valent linking group, R²Is C1-C8 alkylene, - [ CH (R)⁵)-CH(R⁶)-O]_x-CH(R⁵)-CH(R⁶) -or- [ (CH)₂)_y-O]_z-(CH₂)_y-an organic radical having a valence of 2, R³And R⁴Each independently represents an optionally substituted chain or cyclic hydrocarbon group, or R³And R⁴Bonded to each other to form a ring structure. R⁵And R⁶Each independently is a hydrogen atom or a methyl group.

x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

Examples of the 2-valent linking group Q of the general formula (I) include: alkylene having 1 to 10 carbon atoms, arylene, CONH-group, COO-group, ether having 1 to 10 carbon atoms (-R '-OR' -, wherein R 'and R' are each independently an alkylene group), combinations thereof, and the like. Among them, Q is preferably a-COO-group or a-CONH-group from the viewpoints of heat resistance of the obtained polymer, solubility to Propylene Glycol Monomethyl Ether Acetate (PGMEA) which is suitable as a solvent, and relatively inexpensive materials.

A 2-valent organic radical R of the formula (I)²Is C1-C8 alkylene, - [ CH (R)⁵)-CH(R⁶)-O]_x-CH(R⁵)-CH(R⁶) -or- [ (CH)₂)_y-O]_z-(CH₂)_y-. The alkylene group having 1 to 8 carbon atoms may be linear or branched, and examples thereof include: methylene, ethylene, trimethylene, propylene, various butylene, various pentylene, various hexylene, various octylene, and the like.

R⁵And R⁶Each independently is a hydrogen atom or a methyl group.

As the above-mentioned R²From the viewpoint of dispersibility, the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, wherein R is²More preferred are methylene, ethylene, propylene and butylene, and particularly preferred are methylene and ethylene。

R as the above general formula (I)³、R⁴Examples of the cyclic structure formed by bonding to each other include a monocyclic ring of a five-to seven-membered nitrogen-containing heterocycle, and a condensed ring obtained by condensing 2 of these. The nitrogen-containing heterocyclic ring preferably has no aromaticity, and is more preferably a saturated ring.

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

In the block portion composed of the repeating unit having a tertiary amine, the structural unit represented by the general formula (I) preferably contains 3 or more. Among them, from the viewpoint of improving dispersibility and dispersion stability, the content is preferably 3 to 100, more preferably 3 to 50, and particularly preferably 3 to 30.

In the block copolymer containing a block unit composed of the repeating unit having a tertiary amine (hereinafter, sometimes referred to as "a block") and a block unit having solvent affinity (hereinafter, sometimes referred to as "B block"), the block unit having solvent affinity does not have the structural unit represented by the general formula (I) from the viewpoint of improving solvent affinity and improving dispersibility, but contains a solvent affinity block unit having a structural unit copolymerizable with the general formula (I). In the present invention, the arrangement of the blocks of the block copolymer is not particularly limited, and may be, for example: AB block copolymers, ABA block copolymers, BAB block copolymers, and the like. Among them, an AB block copolymer or an ABA block copolymer is preferable from the viewpoint of excellent dispersibility.

The B block may be the same as the B block disclosed in International publication No. 2016/104493.

The number of the constitutional units constituting the block portion having affinity for the solvent may be appropriately adjusted within the range in which the dispersibility of the color material is improved. Among them, the number of the constitutional units constituting the block portion having solvent affinity is preferably 10 to 200, more preferably 10 to 100, and further preferably 10 to 70, from the viewpoint of effectively functioning the solvent affinity portion and the color material affinity portion and improving the dispersibility of the color material.

The solvent-compatible block portion may be selected so as to function as a solvent-compatible site, and the repeating unit constituting the solvent-compatible block portion may be composed of 1 kind, or may contain 2 or more kinds of repeating units.

In the block copolymer used as the dispersant of the present invention, the ratio m/n of the number m of the structural units represented by the general formula (I) to the number n of the units of the other structural units constituting the solvent-compatible block portion is preferably in the range of 0.01 to 1, and more preferably in the range of 0.05 to 0.7 from the viewpoints of color material dispersibility and dispersion stability.

Among them, the dispersant of the present invention preferably contains a polymer having a structure represented by the above general formula (I) and an amine value of 40mgKOH/g to 120mgKOH/g, from the viewpoints of good dispersibility, no foreign matter precipitation during the formation of a coating film, and improved brightness and contrast.

When the amine value is within the above range, the viscosity is excellent in stability with time and heat resistance, and also excellent in alkali developability and solvent resolubility. When the amine value of the dispersant is high, dispersibility and dispersion stability are improved, solvent solubility and solvent re-solubility are improved, compatibility with other components is improved, linearity of a fine line pattern of a colored layer is improved, and jaggies of micropores are easily suppressed. In the present invention, the amine value of the dispersant is particularly preferably 80mgKOH/g or more, and more preferably 90mgKOH/g or more. On the other hand, the amine value of the dispersant is preferably 110mgKOH/g or less, more preferably 105mgKOH/g or less, from the viewpoint of solvent re-solubility.

The amine value is the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in sample 1g, and can be measured by the method defined in JIS-K7237. When the amine value is measured by this method, the amine value of the block copolymer itself used as the dispersant can be measured because the organic acid compound in the dispersant is usually dissociated even by the amino group forming a salt with the organic acid compound.

The acid value of the dispersant used in the present invention is preferably 1mgKOH/g or more as the lower limit from the viewpoint of the effect of suppressing development residue. Among them, the acid value of the dispersant is more preferably 2mgKOH/g or more from the viewpoint of more excellent effect of suppressing the development residue. The acid value of the dispersant used in the present invention is preferably 18mgKOH/g or less as the upper limit of the acid value of the dispersant, from the viewpoint of preventing deterioration of development adhesion and solvent resolubility, improving the linearity of the colored layer fine line pattern, and easily suppressing jaggies of micropores. Among these, the acid value of the dispersant is more preferably 16mgKOH/g or less, and still more preferably 14mgKOH/g or less, from the viewpoint of satisfactory development adhesion and solvent re-solubility.

In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 1mgKOH/g or more, more preferably 2mgKOH/g or more. This is because the effect of suppressing the development residue is improved. The upper limit of the acid value of the block copolymer before salt formation is preferably 18mgKOH/g or less, more preferably 16mgKOH/g or less, and still more preferably 14mgKOH/g or less. This is because the development adhesion and the solvent resolubility are good.

In the present invention, the glass transition temperature of the dispersant is preferably 30 ℃ or higher from the viewpoint of improving development adhesion. That is, the glass transition temperature of the dispersant is preferably 30 ℃ or higher, regardless of whether the dispersant is a block copolymer before salt formation or a salt-type block copolymer. When the glass transition temperature of the dispersant is too low, particularly near the temperature of the developer (usually about 23 ℃), the development adhesion may be lowered. This is presumably because, when the glass transition temperature is close to the developer temperature, the movement of the dispersant during development becomes large, and as a result, the development adhesion is deteriorated. It is presumed that when the glass transition temperature is 30 ℃ or more, the molecular movement of the dispersant during development is suppressed, and thus the reduction of development adhesion is suppressed.

The glass transition temperature of the dispersant is particularly preferably 32 ℃ or higher, and more preferably 35 ℃ or higher, from the viewpoint of development adhesion. On the other hand, from the viewpoint of ease of handling in use such as ease of accurate weighing, it is preferably 200 ℃ or lower.

The glass transition temperature of the dispersant in the present invention can be determined by Differential Scanning Calorimetry (DSC) in accordance with JIS K7121.

The glass transition temperature (Tg) of the block portion and the block copolymer can be calculated by the following formula.

1/Tg＝∑(Xi/Tgi)

The block is formed by copolymerizing n monomer components, i being 1 to n. Xi is the weight fraction of the ith monomer (Σ Xi ═ 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the ith monomer. Where Σ is set such that i is the sum of 1 to n. The value of the homopolymer glass transition temperature (Tgi) of each monomer may be Polymer Handbook (3)^rdEdition) (j.brandrup, e.h. immergut, Wiley-Interscience, 1989)).

When the concentration of the color material is increased and the content of the dispersant is increased, the binder amount is relatively decreased, and therefore, the colored resin layer is easily peeled from the underlying substrate during development. The dispersant contains a B block containing a structural unit derived from a carboxyl group-containing monomer and has the above-mentioned specific acid value and glass transition temperature, and thus the development adhesion is improved. It is presumed that when the acid value is too high, although the developability is excellent, the polarity is too high, and conversely, peeling is likely to occur during development.

As described above, it has been found that, from the viewpoint of suppressing the generation of development residues, simultaneously, having excellent solvent re-solubility and further having high development adhesion, and from the viewpoint of easily forming micropores having excellent shapes, easily suppressing the jaggy of the micropores, and easily forming development residues, the dispersant of the present invention is preferably a polymer having a structure represented by the general formula (I) and having an amine value of 40mgKOH/g or more and 120mgKOH/g or less, an acid value of 1mgKOH/g or more and 18mgKOH/g or less, and a glass transition temperature of 30 ℃ or more, when a colored resin composition containing an oxime ester compound represented by the general formula (1) is formed.

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

The content of the structural unit derived from the carboxyl group-containing monomer in the block copolymer before salt formation is not particularly limited as long as it is appropriately set so that the acid value of the block copolymer is within the above-described specific acid value range, but is preferably 0.05 to 4.5% by mass, more preferably 0.07 to 3.7% by mass, based on the total mass of the total structural units of the block copolymer.

When the content ratio of the structural unit derived from the carboxyl group-containing monomer is not less than the lower limit, the effect of suppressing the development residue is exhibited, and when the content ratio of the structural unit derived from the carboxyl group-containing monomer is not more than the upper limit, the deterioration of the development adhesion and the deterioration of the solvent resolubility can be prevented.

The structural unit derived from the carboxyl group-containing monomer may be composed of 1 type or may contain 2 or more types of structural units as long as the structural unit can have the above-mentioned specific acid value.

From the viewpoint of setting the glass transition temperature of the dispersant used in the present invention to a specific value or higher and improving development adhesion, the total of the monomers having a homopolymer glass transition temperature value (Tgi) of 10 ℃ or higher in the B block is preferably 75 mass% or higher, and more preferably 85 mass% or higher.

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

The weight average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 to 20000, more preferably 2000 to 15000, and particularly preferably 3000 to 12000, from the viewpoint of good color material dispersibility and dispersion stability.

Here, the weight average molecular weight (Mw) was determined as a standard polystyrene equivalent value by Gel Permeation Chromatography (GPC). The macromonomer, the salt-type block copolymer, and the graft copolymer which are the raw materials of the block copolymer are also subjected to the above-mentioned conditions.

Specific examples of the block copolymer containing a block moiety composed of a repeating unit having a tertiary amine and a block moiety having affinity for a solvent include, for example, a block copolymer described in japanese patent No. 4911253.

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

In the present invention, it is also preferable to use, as the dispersant, a polymer containing at least a part of the amino groups of the polymer having a repeating unit of a tertiary amine and a salt formed with an organic acid compound or a halogenated hydrocarbon (hereinafter, such a polymer is referred to as a "salt polymer") from the viewpoint of dispersibility of the color material and dispersion stability.

Among them, from the viewpoint of excellent color material dispersibility and dispersion stability, it is preferable that the polymer containing a repeating unit having a tertiary amine is a block copolymer, and the organic acid compound is an acidic organophosphorus compound such as phenylphosphonic acid or phenylphosphinic acid. Specific examples of the organic acid compound used in the dispersant include, for example, those described in Japanese patent laid-open No. 2012-236882 and the like.

The halogenated hydrocarbon is preferably at least 1 of a halogenated allyl group such as allyl bromide (allyl bromide) or benzyl chloride, and a halogenated aralkyl group, from the viewpoint of excellent color material dispersibility and dispersion stability.

The content of the dispersant is not particularly limited as long as the color material can be uniformly dispersed, and for example, 1 to 40% by mass based on the total solid content of the photosensitive colored resin composition for color filters can be used. The amount of the pigment is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, based on the total solid content of the photosensitive colored resin composition for color filters. When the lower limit value is not less than the above lower limit value, the dispersibility and dispersion stability of the color material are excellent, and the storage stability of the photosensitive colored resin composition for color filters is further excellent. When the content is not more than the above upper limit, the developability is good. In particular, when a colored layer having a high color material concentration is formed, the dispersant is preferably blended in a proportion of 2 to 25% by mass, more preferably 3 to 20% by mass, based on the total solid content of the photosensitive colored resin composition for color filters.

[ antioxidant ]

The photosensitive colored resin composition for color filters of the present invention may further contain an antioxidant. The photosensitive colored resin composition for color filters of the present invention can improve heat resistance and suppress a decrease in luminance after exposure and post-baking by containing an antioxidant in combination with the oxime ester compound represented by the general formula (1), and can form fine pores of a desired shape more easily because excessive radical chain reaction in the fine pores can be controlled without impairing curability when the fine pores are formed by a cured film.

The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known antioxidants. Specific examples of the antioxidant include: hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like, and hindered phenol antioxidants are preferably used from the viewpoint of heat resistance and good pore shape.

The "hindered phenol antioxidant" is an antioxidant having a structure in which at least 1 phenol structure is contained and at least 1 of the 2-position and 6-position of the hydroxyl group of the phenol structure is substituted with a substituent having 4 or more carbon atoms.

Specific examples of the hindered phenol antioxidant include: dibutylhydroxytoluene (BHT), pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX 1010, manufactured by BASF), 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114, manufactured by BASF), 2, 4, 6-tris (4-hydroxy-3, 5-di-tert-butylbenzyl) mesitylene (trade name: IRGANOX 1330, manufactured by BASF), 6- (4-hydroxy-3, 5-di-tert-butylanilino) -2, 4-bis (octylthio) -1, 3, 5-triazine (trade name: IRGANOX 565, manufactured by BASF), 2' -thiodiethylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX 1035, BASF), 1, 2-bis [3- (4-hydroxy-3, 5-di-t-butylphenyl) propionyl ] hydrazine (trade name: IRGANOX MD1024, manufactured by BASF), octyl 3- (4-hydroxy-3, 5-diisopropylphenyl) propionate (trade name: IRGANOX 1135, manufactured by BASF), 4, 6-bis (octylthiomethyl) -o-cresol (trade name: manufactured by IRGANOX 1520L, BASF), N' -hexamethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide ] (trade name: IRGANOX 1098, manufactured by BASF), 1, 6-hexanediol bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (trade name: IRGANOX259 manufactured by BASF), 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ]2, 4, 8, 10-tetraoxaspiro [5.5] undecane (trade name: ADK STABA0-80 manufactured by ADEKA), bis (3-tert-butyl-4-hydroxy-5-methylpropanoic acid) ethylenebis (oxyethylene) (trade name: IRGANOX 245, manufactured by BASF), 1, 3, 5-tris [ [4- (1, 1-dimethylethyl) -3-hydroxy-2, 6-dimethylphenyl ] methyl ] -1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H) -trione (trade name: IRGANOX 1790, manufactured by BASF), 2' methylenebis (6-tert-butyl-4-methylphenol) (trade name: SUMIRAIZA MDP-S, manufactured by sumitomo chemical), 6' -thiobis (2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF), diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate (trade name: irgamo 195, manufactured by BASF), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl acrylate (trade name: SUMIRAIZA GM manufactured by sumitomo chemical), 4' -thiobis (6-t-butyl-m-cresol) (trade name: SUMIRAIZA WX-R, manufactured by sumitomo chemical), 6 '-di-tert-butyl-4, 4' -butylidenedicresol (trade name: ADEKA STAB AO-40, manufactured by ADEKA), etc. Other oligomer-type and polymer-type compounds having a hindered phenol structure, and the like may also be used.

In the present invention, as the antioxidant, a latent antioxidant may be used. The "latent antioxidant" of the present invention is a compound having a protecting group which can be released by heating, and is a compound which exhibits an antioxidant function by releasing the protecting group. Among these, compounds from which a protecting group is easily released by heating at 150 ℃ or higher are preferable. Since the latent antioxidant does not have an antioxidant function at the time of exposure, radicals generated from the photoinitiator are not inactivated, and thus it is easy to suppress sensitivity reduction, suppress line width narrowing, and increase the residual film rate. On the other hand, in the heating step performed after exposure, since the protective group is released to exhibit an antioxidant effect, discoloration of a color material or the like is suppressed, and a colored layer with high brightness can be obtained.

The latent antioxidant suitably used in the present invention includes, from the viewpoint of heat resistance and from the viewpoint of improving the shape of micropores, a latent hindered phenol antioxidant in which a phenolic hydroxyl group of a hindered phenol antioxidant is protected with a protecting group which can be detached by heating, and specific examples thereof include, but are not limited to, the following chemical formulae (a) to (c).

[ chemical formula 11]

Chemical formula (a)

Chemical formula (b)

Chemical formula (c)

The method for producing the latent antioxidant is not particularly limited, and for example, the latent antioxidant can be obtained by reacting a phenolic compound produced by the methods described in Japanese patent laid-open Nos. 57-111375, 3-173843, 6-128195, 7-206771, 7-252191 and 2004-501128 with an acid anhydride, an acid chloride, a Boc reagent, a haloalkane compound, a chlorosilane compound, an allyl ether compound or the like. Further, commercially available products may be used.

Examples of the protective group which can be released by heating include: the reactive residue of an acid anhydride, an acid chloride, a Boc-reacting reagent, a haloalkane compound, a chlorosilane compound, or an allyl ether compound, and typically, a t-butoxycarbonyl group is exemplified.

The content of the antioxidant in the case of using the antioxidant is not particularly limited, and may be, for example, 0.1 to 20% by mass based on the total solid content of the photosensitive colored resin composition for color filters. In addition, from the viewpoint of sufficiently exhibiting the effect of using the photoinitiator in combination, the content is preferably 0.2 to 10% by mass, more preferably 0.3 to 5% by mass, based on the total solid content of the photosensitive colored resin composition for color filters.

In addition, when the photosensitive colored resin composition for color filters of the present invention further contains an antioxidant, from the viewpoint of sufficiently exerting the effect of being used in combination with the photoinitiator, the amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more, based on 100 parts by mass of the total of the photoinitiators used in the present invention.

On the other hand, from the viewpoint of maintaining appropriate sensitivity, the amount is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less, based on 100 parts by mass of the total amount of the photoinitiators used in the present invention.

[ optional additional Components ]

The photosensitive colored resin composition for color filters may contain various additives as needed. Examples of additives include: polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.

Specific examples of the surfactant and the plasticizer include those described in Japanese patent laid-open publication No. 2013-029832.

The ratio of the mass (P) of the color material used in the present invention to the mass (V) of the solid component other than the color material (hereinafter, also referred to as "P/V ratio") is not particularly limited as long as a desired color development can be performed when forming the colored layer of the color filter, and is preferably in the range of 0.05 to 1.00, more preferably in the range of 0.10 to 0.80, further preferably in the range of 0.15 to 0.75, and particularly preferably in the range of 0.20 to 0.70. When the P/V ratio is within the above range, a photosensitive color resin composition for a color filter capable of forming a color layer capable of performing desired color development can be obtained, and the composition can be uniformly dispersed in the photosensitive color resin composition for a color filter.

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

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

In the case of a blue colored resin composition, the P/V ratio is preferably 0.24 or more, more preferably 0.34 or more, and still more preferably 0.41 or more, from the viewpoint of desired color development. Further, it is preferably 1.0 or less. When the lower limit value is not less than the above lower limit value, the color density of the photosensitive colored resin composition for a color filter can be increased, and a color filter pixel can have a higher color rendering and a lower film thickness. In addition, when the respective values are not more than the upper limit, a colored layer having sufficient hardness and adhesion to the substrate can be obtained while having excellent storage stability.

< method for producing photosensitive colored resin composition for color filter >

The method for producing the photosensitive colored resin composition for color filters of the present invention preferably contains a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, a preferable dispersant, an antioxidant, and various additive components used as needed, and the color material can be uniformly dispersed in the solvent by the dispersant, and the method can be prepared by mixing the components using a known mixing means, from the viewpoint of improving the contrast.

Examples of the method for producing the resin composition include: (1) a method of preparing a dispersion liquid of a color material by adding the color material and a dispersant to a solvent, and mixing an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive components used as needed with the dispersion liquid; (2) a method of simultaneously adding a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additive components used as needed to a solvent and mixing them; (3) a method in which a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives used as needed are added to a solvent, mixed, and then a color material is added and dispersed; (4) a method of adding a color material, a dispersant and an alkali-soluble resin to a solvent to prepare a color material dispersion, and further adding and mixing an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additive components used as needed to the dispersion.

Among these methods, the methods (1) and (4) are preferable from the viewpoint of effectively preventing the color material from aggregating and uniformly dispersing it.

The method for preparing the color material dispersion can be appropriately selected from conventionally known dispersion methods. For example: (1) the dispersant solution is prepared by mixing the dispersant in a solvent and stirring the mixture, and then the salt is formed by the amino group of the dispersant and the organic acid compound by mixing the organic acid compound as needed. A method of mixing the resulting mixture with a color material and, if necessary, other components and dispersing the mixture by using a known stirrer or disperser; (2) a method in which a dispersant is mixed with a solvent and stirred to prepare a dispersant solution, and then a color material, an organic acid compound if necessary, and other components if necessary are mixed and dispersed using a known stirrer or a dispersing machine; (3) a method in which a dispersant is mixed in a solvent and stirred to prepare a dispersant solution, then a color material and other components as necessary are mixed, a dispersion is formed using a known stirrer or a dispersing machine, and then an organic acid compound is added as necessary.

Examples of the dispersing machine for performing the dispersing process include: roll mills such as twin-roll mills, three-roll mills, etc.; ball mills such as ball mills and vibration ball mills; a coating material dispenser, a continuous disk bead mill, a continuous ring bead mill and the like. As the preferable dispersing condition of the bead mill, the bead diameter to be used is preferably 0.03mm to 2.00mm, more preferably 0.10mm to 1.0 mm.

Color filter II

The color filter of the present invention is a color filter comprising at least a substrate and colored layers provided on the substrate, wherein at least 1 of the colored layers is a colored layer composed of a cured product of the photosensitive colored resin composition for color filters of the present invention.

Such a color filter of the present invention will be 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. Referring to fig. 1, a color filter 10 of the present invention includes a substrate 1, a light-shielding portion 2, and a colored layer 3.

(colored layer)

At least 1 of the colored layers used in the color filter of the present invention is a colored 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 described below, and is usually formed of a colored pattern of 3 colors or more.

The arrangement of the colored layers is not particularly limited, and may be, for example, a stripe type, a mosaic type, a triangular type, a 4-pixel arrangement type, or other common arrangements. The width, area, and the like of the colored layer can be set arbitrarily.

The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the photosensitive colored resin composition for color filters, but is preferably in the range of 1 μm to 5 μm in general.

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

First, the photosensitive colored resin composition for color filters of the present invention is applied to a substrate to be described later by using application means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, a die coating method, or the like, to form a wet coating film. Among them, spin coating and die coating can be preferably used.

Next, the wet coating film is dried using a hot plate, an oven, or the like, and then exposed to light through a mask having a predetermined pattern, whereby a cured coating film is formed by photopolymerization of an alkali-soluble resin, a photopolymerizable compound, or the like. Examples of the light source used for exposure include: ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, electron beams, and the like. The exposure amount is appropriately adjusted according to the light source used, the thickness of the coating film, and the like.

After the exposure, a heat treatment may be performed to promote the polymerization reaction. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition for color filters to be used, the thickness of the coating film, and the like.

Next, a developing treatment is performed using a developing solution to dissolve and remove the unexposed portion, thereby forming a coating film in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. An appropriate amount of a surfactant or the like may be added to the alkali solution.

In addition, the developing method may employ a general method.

After the development treatment, the cured coating film of the photosensitive color resin composition for color filters is usually cleaned with a developer and dried to form a color layer. After the development treatment, a heating treatment may be performed to sufficiently cure the coating film. The heating conditions are not particularly limited, and may be appropriately selected depending on the application of the coating film.

In the case where the Color Filter of the present invention is formed into a Color Filter on Array (COA) structure, for example, the colored layer may be formed with fine holes during the development treatment. In the present invention, since the photosensitive colored resin composition for a color filter is used, desired fine holes can be easily formed in a colored layer. The shape of the micropores is not particularly limited and may be appropriately selected depending on the application, and in the present invention, micropores having a size of, for example, about 10 μm × 10 μm to 30 μm × 30 μm may be formed. The shape of the micropores is not particularly limited, and examples thereof include a circle, an ellipse, and a polygon.

As a method for forming the fine holes in the colored layer, for example, a method of using a pattern photomask in which a fine mask for forming the fine holes is arranged in an opening pattern of a pattern photomask capable of forming a fine line pattern as a photomask used for forming the colored layer is mentioned.

(shading portion)

The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate described below, and may be the same as a member used as the light-shielding portion in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like. The light shielding portion can be formed with a thin metal film of chromium or the like by sputtering, vacuum deposition, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by developing using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like.

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

(substrate)

As the substrate, a transparent substrate, a silicon substrate, or a substrate in which a thin film of aluminum, silver/copper/palladium alloy, or the like is formed on the transparent substrate or the silicon substrate, which will be described later, can be used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.

The transparent substrate in 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 in a general color filter can be used. Specifically, there may be mentioned: a transparent rigid material having no flexibility such as quartz glass, alkali-free glass, or synthetic quartz plate, or a transparent flexible material having flexibility such as transparent resin film, optical resin plate, or flexible glass.

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

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

III. display device

The display device of the present invention is characterized by having the color filter of the present invention described above. The structure of the display device of the present invention is not particularly limited, and may be appropriately selected from conventionally known display devices, and examples thereof include 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 in that: the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate are provided.

The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As illustrated in fig. 2, a liquid crystal display device 40 of the present invention includes: a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 2, and may be a configuration known as a liquid crystal display device that generally uses a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be employed. Examples of such a driving method include: TN (Twisted Nematic) system, IPS (In-Plane Switching) system, OCB (Optically Compensated Birefringence) system, MVA (Multi-Domain Vertical Alignment) system, and the like. In the present invention, any of these modes can be suitably used.

The counter substrate may be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention and the like.

As a method for forming the liquid crystal layer, a method which can be generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method, a liquid crystal dropping method, and the like. After the liquid crystal layer is formed by the above method, the liquid crystal cell is slowly cooled to room temperature, whereby the enclosed liquid crystal can be aligned.

[ organic light emitting display device ]

An organic light-emitting display device is characterized by having the color filter and the organic light-emitting body of the present invention described above.

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

Examples of the method for stacking the organic light-emitting bodies 80 include: a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 on the upper surface of the color filter; a method of bonding the organic light emitting body 80 formed on the other substrate to the inorganic oxide film 60. In the organic light-emitting body 80, known components can be used as appropriate for 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, and other components. The organic light emitting display device 100 manufactured in the above manner can also be applied to, for example, a passive driving type organic EL display and an active driving type organic EL display.

The organic light emitting display device of the present invention is not limited to the organic light emitting display device having the configuration shown in fig. 3, and may be any one of those conventionally known as an organic light emitting display device using a color filter.

Examples

Hereinafter, examples of the present invention will be described in detail. However, the present invention is not limited to these descriptions.

The structure of the obtained compound was determined by using a nuclear magnetic resonance apparatus (Bruker BioSpin, AVANCEIII HD500MHz)¹H-and¹³the C-NMR spectrum was analyzed and confirmed by mass spectrometry using a liquid chromatography mass spectrometer (Shimadzu corporation, LC-30A, Bruker Daltonics, MicroOTOFQ 2).

(Synthesis example 1: Synthesis of Compound A)

(1) Synthesis of intermediate A1

Fluorene 0.60mol, potassium hydroxide 2.4mol and potassium iodide 0.06mol were dissolved in anhydrous dimethylsulfoxide 500ml under a nitrogen atmosphere, and 1.33mol of bromobutane was slowly added over 2 hours while maintaining at 15 ℃, and the reaction mixture was stirred at 15 ℃ for 1 hour. Then, 2L of distilled water was added to the reaction mixture, and after stirring for about 30 minutes, the product was extracted with 2L of methylene chloride, and the extracted organic layer was washed with 2L of distilled water 2 times. Then, the recovered organic layer was extracted with anhydrous MgSO₄The product was obtained by drying and distilling the solvent under reduced pressure, and purified by silica gel column chromatography (developing solvent: ethyl acetate: n-hexane: 1: 20), whereby the following intermediate a1 was obtained.

[ chemical formula 12]

Intermediate A1

(2) Synthesis of intermediate A2

The above intermediate A1(0.11mol) was dissolved in 500ml of methylene chloride, cooled to-5 ℃ and then 0.13mol of AlCl was slowly added₃A solution containing 15ml of methylene chloride and 0.13mol of cyclohexylpropionyl chloride was slowly added dropwise over 1 hour in such a manner that the temperature of the reaction mixture did not rise, and stirred at-5 ℃ for 1 hour. Then, the reaction mixture was slowly poured into 500mL of ice water, and after stirring for 30 minutes, the organic layer was washed with 200mL of distilled water. Then, the recovered organic layer was distilled under reduced pressure to obtain a product, which was purified by silica gel column chromatography (developing solvent:ethyl acetate: n-hexane ═ 1: 4) purification was performed, whereby the following intermediate a2 was obtained.

[ chemical formula 13]

Intermediate A2

(3) Synthesis of intermediate A3

The above intermediate A2(0.042mol) was dissolved in 200ml of Tetrahydrofuran (THF), 25ml of (4N) HCl dissolved in 1, 4-dioxane and 0.063mol of isobutyl nitrite were successively added, and the reaction mixture was stirred at 25 ℃ for 6 hours. Then, 200ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes to separate an organic layer, followed by washing with 200ml of distilled water. Then, the recovered organic layer was extracted with anhydrous MgSO₄The product was obtained by drying and distilling the solvent under reduced pressure, and purified by silica gel column chromatography (developing solvent: ethyl acetate: n-hexane: 1: 4), whereby the following intermediate a3 was obtained.

[ chemical formula 14]

Intermediate A3

(4) Synthesis of Compound A

The above intermediate A3(0.056mol) was dissolved in 200ml of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, and 0.068mol of triethylamine was added thereto while maintaining at-5 ℃ to stir the reaction solution for 30 minutes. Then, a solution containing 0.068mol of acetyl chloride and 10ml of N-methyl-2-pyrrolidone was slowly added over 30 minutes, and the reaction mixture was stirred for 30 minutes without increasing the temperature. Then, 200ml of distilled water was slowly added to the reaction and stirred for 30 minutes to separate an organic layer. Then, the recovered organic layer was extracted with anhydrous MgSO₄The solvent was dried and distilled under reduced pressure to obtain a product, which was recrystallized from 1L of ethanol and then dried to obtain the following compound a.

[ chemical formula 15]

Compound A

(Synthesis example 2: Synthesis of Compound B)

(1) Synthesis of intermediate B1

The following intermediate B1 was obtained in the same manner as in (1) of synthesis example 1, except that in (1) of synthesis example 1, bromoethane was used in an equimolar amount instead of bromobutane, and purification by silica gel column chromatography was not performed.

[ chemical formula 16]

Intermediate B1

(2) Synthesis of intermediate B2

The following intermediate B2 was obtained in the same manner as in (2) of synthesis example 1, except that in (2) of synthesis example 1, an equimolar amount of the above-mentioned intermediate B1 was used in place of the intermediate a1, and an equimolar amount of propionyl chloride was used in place of the cyclohexylpropionyl chloride.

[ chemical formula 17]

Intermediate B2

(3) Synthesis of intermediate B3

The following intermediate B3 was obtained in the same manner as in (3) of synthesis example 1, except that in (3) of synthesis example 1, the intermediate B2 was used in an equimolar amount instead of the intermediate a2, and a mixed solvent of ethyl acetate and n-hexane (1: 6) was used in place of silica gel column chromatography, and the mixture was recrystallized and then dried to purify the product.

[ chemical formula 18]

Intermediate B3

(4) Synthesis of Compound B

The following compound B was obtained in the same manner as in (4) of synthesis example 1, except that an equimolar amount of intermediate B3 was used instead of intermediate A3 in (4) of synthesis example 1.

[ chemical formula 19]

Compound B

(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 (2) of synthesis example 2, butyryl chloride was used in an equimolar amount instead of propionyl chloride.

[ chemical formula 20]

Compound C

(Synthesis example 4 Synthesis of Compound D)

(1) Synthesis of intermediate D1

0.030mol of 9H-fluoren-2-yl- (phenyl) methanone was dissolved in 45ml of methylene chloride, cooled to-5 ℃ and anhydrous 0.033mol of AlCl was added₃Thereafter, a solution containing 9ml of dichloromethane and 0.033mol of propionyl chloride was slowly added over 1 hour in such a manner that the temperature of the reaction did not rise, and stirred at-5 ℃ for 1 hour. Then, the reaction mixture was slowly poured into 250g of ice water, stirred for 30 minutes, and then the organic layer was separated and washed with 100ml of distilled water. Then, the recovered organic layer was distilled under reduced pressure to obtain a product, which was recrystallized from 20ml of a mixed solution of toluene and ethyl acetate (5: 1), to obtain the following intermediate D1.

[ chemical formula 21]

Intermediate D1

(2) Synthesis of intermediate D2

The above intermediate D1(0.010mol) was dissolved in 30ml of Tetrahydrofuran (THF), 4.5ml of (4N) HCl dissolved in 1, 4-dioxane and 0.015mol of isoamyl nitrite were successively added, and the reaction mixture was stirred at 25 ℃ for 24 hours. Then, 20ml of ethyl acetate and 50ml of distilled water were added to the reaction solution to extract an organic layer. The extracted organic layer was extracted with anhydrous MgSO₄The resulting product was recrystallized from 30ml of a mixed solvent of ethanol and ethyl acetate (5: 1), and then dried, thereby obtaining the following intermediate D2.

[ chemical formula 22]

Intermediate D2

(3) Synthesis of Compound D

The intermediate D2(0.006mol) was dissolved in 25ml of ethyl acetate under a nitrogen atmosphere, the reaction mixture was maintained at-5 ℃, 0.007mmol of triethylamine was added, and after stirring the reaction solution for 30 minutes, a solution containing 0.007mol of acetyl chloride and 5ml of ethyl acetate was slowly added over 30 minutes without increasing the temperature of the reaction mixture, and the mixture was stirred for 30 minutes. Then, 100ml of distilled water was slowly added to the reaction mixture and stirred for about 30 minutes, and the organic layer was separated. Then, the recovered organic layer was extracted with anhydrous MgSO₄Dried, and the solvent was distilled under reduced pressure to obtain the following compound D.

[ chemical formula 23]

Compound D

(Synthesis example 5 Synthesis of Compound E)

(1) Synthesis of intermediate E1

Into a 500ml four-necked flask, 0.2mol of diphenyl sulfide and 0.22mol of A1Cl as pulverized were charged₃And dichloroethane 150ml, stirring, flowing argon, cooling with ice bath, when the temperature drops to 0 ℃, begin to drop containing cyclohexyl propionyl chloride 0.22mol and dichloroethane 42g solution, while adjusting the temperature to 10 ℃, the addition of over 1.5 hours. The temperature was raised to 15 ℃ and stirring was continued for 2 hours, after which the reaction solution was discharged.

After the reaction solution was slowly poured into dilute hydrochloric acid containing 400g of ice and 65ml of concentrated hydrochloric acid under stirring, the lower layer was separated with a separatory funnel, the upper layer was extracted with 50ml of dichloroethane, and the extract and the lower layer were combined. Then, 10g of NaHCO was added₃NaHCO with 200g of water₃The solution was washed with 200ml of water 3 times until the pH was neutral, and 60g of anhydrous MgSO₄After drying to remove water, the dichloroethane was evaporated by rotary evaporation. The solid powder remaining in the rotary evaporation flask was put into 200ml of petroleum ether, suction filtered, and 150ml of anhydrous ethanol was further added, followed by heating and refluxing. Then, the reaction mixture was cooled to room temperature, further cooled with ice for 2 hours, and subjected to suction filtration, followed by drying in an oven at 50 ℃ for 2 hours to obtain the following intermediate E1.

[ chemical formula 24]

Intermediate E1

(2) Synthesis of intermediate E2

Into a 500ml four-necked flask, 42g of the intermediate E1, 400g of tetrahydrofuran, 200g of concentrated hydrochloric acid and 24.2g of isoamyl nitrite were charged, and the mixture was stirred at room temperature for 5 hours, followed by discharging the reaction mixture.

The reaction solution was poured into a large beaker, 1000ml of water was added thereto, and after stirring, the mixture was allowed to stand overnight to be separated into layers, whereby a yellow viscous liquid was obtained. The viscous liquid was extracted with dichloroethane, and 50g of anhydrous MgSO was added₄Drying, vacuum filtering, and rotary evaporating the filtrate to remove solventDose to obtain oily viscous substance. Subsequently, the viscous substance was poured into 150ml of petroleum ether, and stirred, precipitated, and suction-filtered to obtain a white powdery solid. Then, dried at 60 ℃ for 5 hours to obtain the following intermediate E2.

[ chemical formula 25]

Intermediate E2

(3) Synthesis of Compound E

Into a 1000ml four-necked flask, 34g of the above intermediate E2, 350ml of dichloroethane and 12.7g of triethylamine were charged and stirred, and the mixture was cooled in an ice bath, and when the temperature was lowered to 0 ℃, a solution containing 15.7g of acetyl chloride and 15g of dichloroethane was added dropwise over about 1.5 hours. After stirring for 1 hour, 500ml of cold water was added dropwise, and the layers were separated by a separatory funnel. With 5% NaHCO₃Washing the solution with 200ml of water for 1 time, washing with 200ml of water for 2 times until the pH value is neutral, washing with diluted hydrochloric acid prepared by mixing concentrated hydrochloric acid 20g with water 400ml for 1 time, washing with 200ml of water for 3 times, and washing with anhydrous MgSO 100g₄Drying, rotary evaporating to remove solvent to obtain viscous liquid. To the viscous liquid, a proper amount of methanol was added to precipitate a white solid, which was then filtered and dried to obtain the following compound E.

[ chemical formula 26]

Compound E

(Synthesis example 6: Synthesis of Compound F)

The following compound F was synthesized in the same manner as in synthesis example 5, except that [4- (phenylthio) phenyl ] -2-thiophen-one was used in an equimolar amount instead of diphenyl sulfide in (1) of synthesis example 5.

[ chemical formula 27]

Compound F

Synthesis example 7 production of dispersant (Block copolymer A)

250 parts by mass of THF and 0.6 part by mass of lithium chloride were added to a 500mL round-bottom four-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer and a digital thermometer, and nitrogen substitution was sufficiently performed. After the reaction flask was cooled to-60 ℃, 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. Dropwise addition over 60 minutes using an addition funnel: 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 18.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 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 17.5 parts by mass of Methyl Methacrylate (MMA) as monomers for the B block. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) as a monomer for a block was added dropwise over 20 minutes. After 30 minutes of the reaction, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, vacuum-dried to purify, and diluted with PGMEA to a solid content 30 mass% solution. 32.5 parts by mass of water was added, the temperature was raised to 100 ℃ and the reaction was carried out for 7 hours to deprotect the structural unit derived from EEMA to give a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, filtered, and vacuum-dried to purify the solution, and a block copolymer a (acid value 8mgKOH/g, Tg38 ℃) containing an a block having a structural unit represented by the general formula (I) and a B block derived from a carboxyl group-containing monomer and having solvophilicity was obtained. The thus-obtained block copolymer a was confirmed by GPC (gel permeation chromatography), and 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 solution 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 was added dropwise to a polymerization vessel containing 150 parts by mass of PGMEA at 100 ℃ for 3 hours under a nitrogen stream. After the completion of the dropwise addition, the mixture was further heated at 100 ℃ for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7000.

Next, 20 parts by mass of Glycidyl Methacrylate (GMA), 0.2 part by mass of triethylamine, and 0.05 part by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110 ℃ for 10 hours, and air was bubbled through the reaction solution. The obtained alkali-soluble resin a was obtained by introducing a side chain having an olefinic double bond into the main chain obtained by copolymerization of styrene with MMA and MAA using GMA, and had a solid content of 42.6 mass%, an acid value of 74mgKOH/g, and a weight-average molecular weight of 12000. The weight average molecular weight was determined by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. The acid value was measured according to JIS K0070.

(Synthesis example 9 Synthesis of blue Material. alpha.)

(1) Synthesis of intermediate 1

Referring to the production methods of intermediate 3 and intermediate 4 described in international publication No. 2012/144521, 15.9g of intermediate 1 represented by the following chemical formula (1) was obtained (yield 70%).

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

MS (Mass Spectrometry ) (ESI (Electrospray Ionization)) (m/z): 511(+), 2 valent

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

[ chemical formula 28]

Chemical formula (1)

(2) Synthesis of blue Material alpha

5.00g (4.58mmol) of the above intermediate 1 was added to 300ml of water and dissolved at 90 deg.CTo be decomposed into an intermediate 1 solution. Then, phosphotungstic acid n hydrate H₃[PW₁₂O₄₀]·nH₂O (n-30) (manufactured by japan inorganic chemical industry) 10.44g (3.05mmol) was put in 100ml of water, and stirred at 90 ℃ to prepare an aqueous phosphotungstic acid solution. The prepared aqueous phosphotungstic acid solution was mixed with the freshly prepared intermediate 1 solution at 90 ℃ and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain α 13.25g of a blue color material of a metal lake material of triarylmethane-based basic dye represented by the following chemical formula (2).

The obtained compound was confirmed to be the target compound from the following analysis results.

MS (ESI) (m/z): 510(+), 2 price

Elemental analysis value: CHN found (41.55%, 5.34%, 4.32%); theoretical value (41.66%, 5.17%, 4.11%)

[ chemical formula 29]

Chemical formula (2)

Synthesis example 10 preparation of Azo derivative 1

23.1g of diazobarbituric acid (diazobarbituric acid) and 19.2g of barbituric acid were introduced into 550g of distilled water. Next, azobarbituric acid (0.3 mol) was adjusted to azobarbituric acid using an aqueous potassium hydroxide solution, and 750g of distilled water was mixed. 5g of 30% hydrochloric acid are added dropwise. Then, 38.7g of melamine were introduced. Subsequently, 0.39 mol of the nickel chloride solution and 0.21 mol of the zinc chloride solution were mixed and added, and the mixture was stirred at 80 ℃ for 8 hours. The pigment was separated by filtration, washed, dried at 120 ℃ and ground with a mortar to obtain Azo derivative 1 (Azo pigment Ni-Azo-1, Ni: Zn ═ 65: 35 (molar ratio)).

Synthesis example 11 preparation of Azo derivative 2

Azo derivative 2 (Azo pigment Ni-Azo-2, Ni: Zn: 70: 30 (molar ratio) was obtained in the same manner as in synthesis example 10, except that a 0.42 mol nickel chloride solution and a 0.18 mol zinc chloride solution were used instead of the 0.39 mol nickel chloride solution and the 0.21 mol zinc chloride solution in preparation of Azo derivative 1 in synthesis example 10.

Synthesis example 12 preparation of Azo derivative 3

Azo derivative 3 (Azo pigment Ni-Azo-3, Ni: Zn: 50 (molar ratio)) was obtained in the same manner as in synthesis example 10, except that a 0.3 mol nickel chloride solution and a 0.3 mol zinc chloride solution were used instead of the 0.39 mol nickel chloride solution and the 0.21 mol zinc chloride solution in the preparation of Azo derivative 1 in synthesis example 10.

(Synthesis example 13: preparation of Azo derivative 4)

Azo derivative 4 (Azo pigment Ni-Azo-4, Ni: Zn: 30: 70 (molar ratio)) was obtained in the same manner as in synthesis example 10, except that a 0.18 mol nickel chloride solution and a 0.42 mol zinc chloride solution were used instead of the 0.39 mol nickel chloride solution and the 0.21 mol zinc chloride solution in the preparation of Azo derivative 1 in synthesis example 10.

Synthesis example 14 preparation of Azo derivative 5

Azo derivative 5 (Azo pigment Ni-Azo-5, Ni: Zn: 10: 90 (molar ratio)) was obtained in the same manner as in synthesis example 10, except that a 0.06mol nickel chloride solution and a 0.54 mol zinc chloride solution were used instead of the 0.39 mol nickel chloride solution and the 0.21 mol zinc chloride solution in the preparation of Azo derivative 1 in synthesis example 10.

(Synthesis example 15 Synthesis of latent antioxidant (Compound a))

0.01mol of a phenol compound represented by the following chemical formula (3), 0.05mol of di-tert-butyl dicarbonate and 30g of pyridine were mixed, and 0.025mol of 4-dimethylaminopyridine was added thereto under a nitrogen atmosphere at room temperature, followed by stirring at 60 ℃ for 3 hours. After cooling to room temperature, the reaction mixture was poured into 150g of ion-exchanged water, and 200g of chloroform was added thereto to conduct oil-water separation. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100g of methanol was added to the residue to conduct crystallization. The obtained white powdery crystals were dried at 60 ℃ for 3 hours under reduced pressure to obtain a latent antioxidant represented by the above chemical formula (a) (compound a). The structure of the obtained potential antioxidant was confirmed by IR and NMR.

[ chemical formula 30]

Chemical formula (3)

(example 1)

(1) Production of color Material Dispersion 1

5.1 parts by mass of the block copolymer A of Synthesis example 7 as a dispersant, 13.0 parts by mass of the blue color material α obtained in Synthesis example 9 as a color material, 5.1 parts by mass of the alkali-soluble resin A solution obtained in Synthesis example 8 in terms of solid content, 76.8 parts by mass of PGMEA, and 100 parts by mass of 2.0 mm-diameter zirconia beads were charged into a mayonnaise bottle, and shaken for 1 hour by a paint shaker (manufactured by Hakka Seiko Co., Ltd.) to prepare a pre-crushed product, then 2.0 mm-diameter zirconia beads were taken out, 200 parts by mass of 0.1 mm-diameter zirconia beads were added, and similarly dispersed for 4 hours by a paint shaker to prepare a main crushed product, thereby obtaining a color material dispersion 1.

(2) Production of photosensitive colored resin composition 1 for color Filter

286.1 parts by mass of the color material dispersion 1 obtained in (1) above, 8.6 parts by mass of the alkali-soluble resin a solution obtained in synthesis example 8 in terms of solid content, 18.2 parts by mass of a photopolymerizable compound (trade name Aronix M-520D, manufactured by tokyo synthesis corporation), 2.0 parts by mass of dibutylhydroxytoluene (BHT) as an antioxidant, 5.1 parts by mass of the compound a obtained in synthesis example 1 as a photoinitiator, and 42.2 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition 1 for a color filter.

(examples 2 to 13)

Photosensitive colored resin compositions 2 to 13 for color filters were obtained in the same manner as in example 1, except that the photoinitiator used in example 1 was the one having the type and amount shown in Table 1.

In example 8, OXE-01 used as a photoinitiator was an oxime ester photoinitiator (trade name IRGACURE OXE-01, manufactured by BASF) and was a compound represented by the following chemical formula (4).

[ chemical formula 31]

Chemical formula (4)

(example 14)

A photosensitive colored resin composition 14 for a color filter was obtained in the same manner as in example 13 except that a bisphenol antioxidant (manufactured by ADEKA STAB AO-40, manufactured by ADEKA) was used instead of BHT as the antioxidant in example 13.

(example 15)

A photosensitive colored resin composition 15 for a color filter was obtained in the same manner as in example 13 except that in example 13, a hindered phenol antioxidant (Irg1010, manufactured by BASF) was used instead of BHT as the antioxidant.

(example 16)

A photosensitive colored resin composition 16 for a color filter was obtained in the same manner as in example 13 except that the compound a belonging to the latent antioxidant obtained in synthesis example 15 was used as an antioxidant in place of BHT in example 13.

(examples 17 to 21)

Photosensitive colored resin compositions 17 to 21 for color filters were obtained 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 added were changed to the amounts shown in table 1 in example 1.

Comparative examples 1 to 3

Photosensitive colored resin compositions 1 to 3 for color filters were obtained in the same manner as in example 21 except that in example 21, the photoinitiators shown in Table 1 were used instead of the compound A obtained in Synthesis example 1.

The photoinitiator used in comparative example 1 was OXE-02 (manufactured by BASF) represented by the following formula (5):

[ chemical formula 32]

Chemical formula (5)

Comparative example 3 the photoinitiator used was a comparative compound a represented by the following chemical formula (6):

[ chemical formula 33]

Chemical formula (6)

(example 22)

A photosensitive colored resin composition 22 for a color filter was obtained in the same manner as in example 13 except that 37.2 parts by mass of pigment red 254(PR254) was used as the color material in place of the blue color material α in example 13.

Comparative example 4

In example 22, a photosensitive colored resin composition 4 for a comparative color filter was obtained in the same manner as in example 22 except that the compound a obtained in synthesis example 1, the compound E obtained in synthesis example 5, and Irg819 (manufactured by BASF) were not used as a photoinitiator, OXE-02 (manufactured by BASF) represented by the above chemical formula (5) was used in an amount shown in table 2, and 20.2 parts by mass of a photopolymerizable compound was used without using an antioxidant (BHT).

(example 23)

Photosensitive colored resin composition 23 for color filters was obtained in the same manner as in example 13 except that 16.48 parts by mass of pigment green 59(PG59) and 20.72 parts by mass of Azo derivative 1 obtained in synthesis example 10 were used as the color material in place of blue color material α in example 13.

Comparative example 5

In example 23, a photosensitive colored resin composition 5 for a comparative color filter was obtained in the same manner as in example 23 except that the compound a obtained in synthesis example 1, the compound E obtained in synthesis example 5, and Irg819 (manufactured by BASF) were not used as a photoinitiator, OXE-02 (manufactured by BASF) represented by the above chemical formula (5) was used in an amount shown in table 2, and 20.2 parts by mass of a photopolymerizable compound was used without using an antioxidant (BHT).

(example 24)

A photosensitive colored resin composition 24 for a color filter was obtained in the same manner as in example 13, except that in example 13, 37.2 parts by mass of c.i. solvent yellow 162 was used instead of the blue color material α, and 20.2 parts by mass of a photopolymerizable compound was used instead of the antioxidant (BHT).

Comparative example 6

In example 24, a photosensitive colored resin composition 6 for a comparative color filter was obtained in the same manner as in example 24 except that the compound a obtained in synthesis example 1, the compound E obtained in synthesis example 5, and Irg819 (manufactured by BASF) were not used as photoinitiators and OXE-02 (manufactured by BASF) represented by the above chemical formula (5) was used in amounts shown in table 2.

(example 25)

A photosensitive colored resin composition 25 for a color filter was obtained in the same manner as in example 16 except that 23.8 parts by mass of pigment green 58 and 13.4 parts by mass of Azo derivative 2 obtained in synthesis example 11 were used as the color material in place of the blue color material α in example 16.

(example 26)

A photosensitive colored resin composition 26 for a color filter was obtained in the same manner as in example 16 except that 24.5 parts by mass of pigment green 58 and 12.7 parts by mass of Azo derivative 3 obtained in synthesis example 12 were used as the color material in place of the blue color material α in example 16.

(example 27)

A photosensitive colored resin composition 27 for a color filter was obtained in the same manner as in example 16 except that 25.3 parts by mass of pigment green 58 and 11.9 parts by mass of the Azo derivative 4 obtained in synthesis example 13 were used as the color material in place of the blue color material α in example 16.

(example 28)

A photosensitive colored resin composition 28 for a color filter was obtained in the same manner as in example 16, except that 26.1 parts by mass of pigment green 58 and 11.1 parts by mass of the Azo derivative 5 obtained in synthesis example 14 were used as the color material in place of the blue color material α in example 16.

(example 29)

A photosensitive colored resin composition 29 for a color filter was obtained in the same manner as in example 27 except that BHT was used instead of the compound a as an antioxidant in example 27.

(example 30)

A photosensitive colored resin composition 30 for a color filter was obtained in the same manner as in example 27 except that 20.2 parts by mass of the photopolymerizable compound was used instead of the compound a of the antioxidant in example 27.

Comparative example 7

In example 27, a photosensitive colored resin composition 7 for a comparative color filter was obtained in the same manner as in example 27 except that the compound a obtained in synthesis example 1, the compound E obtained in synthesis example 5, and Irg819 (manufactured by BASF) were not used as photoinitiators, OXE-02 (manufactured by BASF) represented by the above chemical formula (5) was used in amounts shown in table 2, and 20.2 parts by mass of a photopolymerizable compound was used without using an antioxidant.

[ evaluation ]

The photosensitive colored resin compositions obtained in the examples and comparative examples were applied to a Glass substrate (NA 35, NH Techno Glass) using a spin coater so that the thickness of the cured coating film was 3.0 μm, and then dried at 80 ℃ for 3 minutes using a hot plate to form a coating film on the Glass substrate. The coating film was patterned with a pattern photomask (chrome mask) having a chrome mask of 20 μm × 20 μm disposed at the center of a thin independent line having an opening size of 90 μm × 300 μm, and the thickness of the coating film was controlled at 40mJ/cm using an ultrahigh-pressure mercury lamp²The ultraviolet light of (3) is exposed to form a post-exposure coating film on the glass substrate. Next, spin coating development was performed using a 0.05 wt% aqueous solution of potassium hydroxide as a developer, and after 60 seconds of contact with the developer, development treatment was performed by washing with pure water to obtain a coating film having a fine isolated line pattern with micropores. Then, post-baking was performed for 25 minutes in a 230 ℃ dust-free oven, thereby forming a separate fine line pattern-shaped colored layer having fine pores. The obtained colored layer was subjected to the following evaluation.

< evaluation of optical Properties >

The photosensitive colored resin compositions obtained in the examples and comparative examples were applied to a Glass substrate (NA 35, NH Techno Glass corporation) by using a spin coater, and then dried at 80 ℃ for 3 minutes by using a hot plate to form a coating film on the Glass substrate. Irradiating the entire surface of the wafer with an ultra-high pressure mercury lamp at 60mJ/cm without a photomask²The ultraviolet ray of (4) to form a coating film after exposure. Next, 0.05 wt% potassium hydroxide aqueous solution was used as a developer to perform spin coating development, and after 60 seconds of contact with the developer, the developer was washed with pure water to perform development treatment, thereby forming a post-development coating film. Then, post-baking was performed in a 230 ℃ dust-free oven for 25 minutes, and with respect to the chroma, when a blue color material α was used, a cured coating (colored layer) was formed so that y was 0.083, when PR254 was used, a cured coating (colored layer) was formed so that x was 0.650, when a PG59/Azo derivative was used, a cured coating (colored layer) was formed so that y was 0.610, when c.i. solvent 162 yellow was used, a cured coating (colored layer) was formed so that y was 0.503, and when a PG58/Azo derivative was used, a cured coating (colored layer) was formed so that y was 0.630. The chromaticity (x, Y) and luminance (Y) of the colored layer were measured by using an Olympus system micro-spectrometer OSP-SP 200.

< evaluation of developability >

[ straightness ]

The width of the colored layer in the portion where the opening width of the chrome mask used for exposure was 90 μm, and the width of the colored layer pattern was measured at 5 places by an optical microscope, and the linearity was evaluated according to the fluctuation of the line width.

A: fluctuation within +/-0.1 mu m

B: the fluctuation is more than +/-0.1 mu m and within +/-0.3 mu m

C: fluctuation exceeding + -0.3 μm

[ residual film ratio ]

In the formation of the colored layer, the film thickness (E) after exposure and the film thickness (D) after development were measured with a stylus type profiler P-16 (manufactured by KLA-Tencor Co.) and the film thickness (D) after development/the film thickness (E) after exposure was calculated as a residual film ratio.

It should be noted that if the film thickness after development (D)/the film thickness after exposure (E) is 90% or more, it falls within a range suitable for practical use.

The colored layer was observed with an optical microscope, and the shape of the micropores, jaggies, and development residue were evaluated according to the following evaluation criteria.

[ shape ]

A: the shift in the size of the micropores formed in the colored layer with respect to the size of the chromium mask disposed in the independent fine line pattern was less than 2% in absolute value

B: the shift in the size of the micropores formed in the colored layer is 2% to 6% in absolute value with respect to the size of the chromium mask disposed in the independent fine line pattern

C: the shift in the size of the micropores formed in the colored layer is greater than 6% and not greater than 8% in absolute value with respect to the size of the chromium mask disposed in the individual fine line pattern

D: the shift in the size of the micropores formed in the colored layer with respect to the size of the chromium mask disposed in the independent fine line pattern was greater than 8% in absolute value

The size deviation is calculated as an average value of the deviation of each side size.

[ sawtooth ]

A: the ten-point average roughness of the periphery of the micropores formed on the colored layer is less than 0.1

B: the ten-point average roughness of the periphery of the micropores formed on the colored layer is 0.1-0.5

C: the ten-point average roughness of the periphery of the micropores formed on the colored layer is more than 0.5

The ten-point average roughness was measured according to JIS B0601.

[ development residue ]

AA: in the observation by an optical microscope, no coloring was observed in the inside of the micropores formed in the colored layer, and no transparent material was observed in the periphery of the micropores

A: in the observation by an optical microscope, although no coloring was observed in the inside of the micropores formed in the coloring layer, a part of the transparent material was observed in the periphery of the micropores

B: in the observation by an optical microscope, coloring was observed inside the micropores formed in the colored layer

The abbreviations in tables 1 and 2 are as follows.

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

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

Irg 369: alpha-amino ketone photoinitiator (IRGACURE 369, BASF)

Irg 907: alpha-amino ketone photoinitiator (IRGACURE 907, BASF)

Mercapto group system: mercapto chain transfer agent (2-mercaptobenzothiazole, Tokyo chemical products)

The diimido series: diimidazole photoinitiator (HABI, manufactured by Blackgold formation)

DETX: thioxanthone photoinitiator (DOUBLECURE DETX, product of Double bond chemical)

1rg 819: acylphosphine oxide photoinitiator (IRGACURE 819, manufactured by BASF)

BHT: dibutylhydroxytoluene

AO-40: bisphenol antioxidant (ADEKA STAB AO-40, manufactured by ADEKA)

Irg 1010: hindered phenol antioxidant (IRGACURE 1010, BASF)

< summary of results >

The photosensitive colored resin compositions of examples 1 to 30 containing the oxime ester compound represented by the general formula (1) as a photoinitiator can form a colored layer having improved brightness as compared with comparative photosensitive colored resin compositions each using the same color material.In addition, the colored resin compositions of examples 1 to 30 had high film residue ratio and good sensitivity. It is known that the photosensitive colored resin compositions of examples 1 to 30 have excellent linearity of the fine line pattern, and that the colored layer is patterned and desired fine holes are easily formed in the colored layer. Examples 1 to 3 using the oxime ester compound of the general formula (1) wherein Z is a hydrogen atom have high luminance and high residual film ratio, and examples 1 to 3 using the oxime ester compound of the general formula (1) wherein Z is ═ C ═ O) R^dIn example 4 of the oxime ester compound of (3), the oxime ester compound was more excellent in solvent solubility and compatibility with other components, and the shape of micropores was more excellent. When the cross sections of the micropores in comparative example 1 and example 2 were observed, the taper angle was gentle in example 2, and the shape of the micropores was more favorable.

In addition, by using the oxime ester compound represented by the general formula (1) and the oxime ester compound having a diphenyl sulfide skeleton in combination as a photoinitiator, the shape of micropores is more favorable (comparison between example 1 and example 5, and comparison between example 2 and examples 6 to 8).

Further, by combining the oxime ester compound represented by the above general formula (1) and an oxime ester compound having a diphenyl sulfide skeleton as a photoinitiator, and further containing at least 1 selected from an α -amino ketone photoinitiator, a diazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent, linearity of a fine line pattern is improved, and a shape of micropores is more favorable (comparison of example 5 with examples 9 to 13).

In addition, by containing an antioxidant, the jaggy of the micropores is further suppressed, and the brightness is also improved (comparison of example 1 with example 21, comparison of examples 27 and 29 with example 30). Among the antioxidants, when a latent antioxidant (compound a) is used, the number of micropores is further suppressed, and the residual film ratio is as good as that in the case where no antioxidant is used. On the other hand, in the case of using a hindered phenol-based antioxidant instead of a latent antioxidant, the brightness was further improved as compared with the case of using a latent antioxidant (comparison of examples 27 and 29 with example 30).

On the other hand, in comparative example 1 and comparative examples 4 to 7 in which an oxime ester compound having a carbazole skeleton was used as a photoinitiator without containing an oxime ester compound represented by the general formula (1), brightness was poor, linearity of a fine line pattern was poor, and micropores could not be formed, as compared with examples using the same color material.

In addition, comparative example 2, which does not contain the oxime ester compound represented by the above general formula (1) but uses Irg907(α -aminoketone photoinitiator) as a photoinitiator, is inferior in brightness and residual film ratio.

Comparative example 3, which does not contain the oxime ester compound represented by the above general formula (1), and uses a comparative compound a having a fluorene skeleton having a nitro group and to which an oxime ester group is not bonded via a carbonyl group, as a photoinitiator, is inferior in brightness and linearity. It is presumed that the poor linearity of comparative example 3 is due to poor solvent solubility and poor compatibility with other components of comparative compound a.

Description of the symbols

1 substrate

2 light-shielding part

3 coloured layer

10 color filter

20 opposed substrate

30 liquid crystal layer

40 liquid crystal display device

50 organic protective layer

60 inorganic oxide film

71 transparent anode

72 hole injection layer

73 hole transport layer

74 luminescent layer

75 electron injection layer

76 cathode

80 organic light-emitting body

100 organic light emitting display device

Claims

1. A photosensitive colored resin composition for color filters, comprising: a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and an antioxidant,

the antioxidant is at least 1 selected from the group consisting of hindered phenol antioxidants and latent hindered phenol antioxidants, the latent hindered phenol antioxidants having a phenolic hydroxyl group of the hindered phenol antioxidants protected by a protecting group releasable by heating,

general formula (1)

In the general formula (1), R^aAnd R^bAre each independently a hydrogen atom or an alkyl group; r^cIs a hydrocarbon group optionally containing at least 1-valent linking group selected from the group consisting of a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (-CO-); z is a hydrogen atom or- (C ═ O) R^d，R^dIs a hydrocarbon group optionally containing at least 1 selected from an oxygen atom and a sulfur atom, or a heterocyclic group containing no nitrogen atom and containing at least 1 selected from an oxygen atom and a sulfur atom; r^eIs a hydrocarbon group having 1 to 10 carbon atoms.

2. The photosensitive colored resin composition for color filters according to claim 1, wherein the photoinitiator contains 2 or more oxime ester compounds having no carbazole skeleton.

3. The photosensitive coloring resin composition for color filters according to claim 1 or 2, wherein the photoinitiator further comprises an oxime ester compound having a diphenyl sulfide skeleton.

4. The photosensitive colored resin composition for color filters according to claim 1 or 2, wherein the photoinitiator further comprises at least 1 selected from the group consisting of an α -amino ketone photoinitiator, a diazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent.

5. The photosensitive colored resin composition for color filters according to claim 1 or 2, wherein the photoinitiator further comprises at least 1 selected from the group consisting of an α -amino ketone photoinitiator, a diazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent, and an oxime ester compound having a diphenyl sulfide skeleton.

6. The photosensitive colored resin composition for color filters according to claim 1 or 2, wherein the photoinitiator further comprises an oxime ester compound having a diphenyl sulfide skeleton represented by general formula (2),

general formula (2)

In the general formula (2), R^c’Is a C6-10 alkyl group composed of a linear alkyl group and a cyclic alkyl group, R^fIs C1-C4 alkyl, Z¹Is hydrogen atom, nitro or- (C ═ O) R^d’，R^d’Is a hydrocarbon group optionally containing at least 1 selected from an oxygen atom and a sulfur atom, or a heterocyclic group containing no nitrogen atom but containing at least 1 selected from an oxygen atom and a sulfur atom.

7. The photosensitive coloring resin composition for color filters according to claim 1 or 2, wherein the photoinitiator further comprises at least 1 selected from the group consisting of an α -amino ketone photoinitiator, a diazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent, and an oxime ester compound having a diphenyl sulfide skeleton represented by the following general formula (2),

general formula (2)

General formula (A)2) In, R^c’Is a C6-10 alkyl group composed of a linear alkyl group and a cyclic alkyl group, R^fIs C1-C4 alkyl, Z¹Is hydrogen atom, nitro or- (C ═ O) R^d’，R^d’Is a hydrocarbon group optionally containing at least 1 selected from an oxygen atom and a sulfur atom, or a heterocyclic group containing no nitrogen atom but containing at least 1 selected from an oxygen atom and a sulfur atom.

8. The photosensitive colored resin composition for color filters according to claim 1 or 2, further comprising a dispersant comprising a polymer having a structure represented by the following general formula (I) and an amine value of 40mgKOH/g or more and 120mgKOH/g or less:

general formula (I)

In the general formula (I), R¹Is a hydrogen atom or a methyl group; q is a direct bond or a 2-valent linking group; r is²Is C1-8 alkylene, - [ CH (R) ]⁵)-CH(R⁶)-O]_x-CH(R⁵)-CH(R⁶) -or- [ (CH)₂)_y-O]_z-(CH₂)_y-a 2-valent organic group as shown; r³And R⁴Each independently represents an optionally substituted chain or cyclic hydrocarbon group, or R³And R⁴Bonded to each other to form a ring structure; r is⁵And R⁶Each independently is a hydrogen atom or a methyl group;

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

9. The photosensitive colored resin composition for color filters according to claim 8, wherein the dispersant is a polymer containing a structure represented by the general formula (I) above, having an amine value of 40mgKOH/g or more and 120mgKOH/g or less, and having an acid value of 1mgKOH/g or more and 18mgKOH/g or less.

10. A photosensitive coloring resin composition for color filters according to claim 1 or 2, wherein the color material comprises a zinc phthalocyanine pigment and a yellow color material, and the yellow color material comprises: at least 1 kind of anion selected from the group consisting of mono-, di-, tri-and tetra-anions of azo compounds represented by the following general formula (ii) and tautomeric structures thereof, and at least 2 kinds of metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn;

general formula (ii)

In the above general formula (ii), R³¹Each independently is OH, NH₂NH-CN, acylamino, alkylamino, or arylamino; r³²Each independently is-OH or-NH₂。

11. A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least 1 of the colored layers is a colored layer comprising a cured product of the photosensitive colored resin composition for color filters according to any one of claims 1 to 10.

12. A display device having the color filter of claim 11.