TWI742166B - Photosensitive color resin composition for color filter, color filter and display device - Google Patents

Abstract

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

Description

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

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

In recent years, with the development of personal computers (special mobile personal computers), the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, and tablet computers) has also increased, showing that the liquid crystal display market is expanding. In addition, recently, organic light-emitting display devices such as organic EL displays that utilize self-luminescence and high visibility have become a new generation of image display devices that have attracted much attention. The performance of these image display devices strongly desires further enhancement of image quality and reduction of power consumption.

These liquid crystal display devices and organic light emitting display devices use color filters. For example, in the formation of a color image in a liquid crystal display device, light passing through a color filter is directly colored into the colors of each pixel constituting the color filter, and then the color light is synthesized to form a color image. In addition to the conventional cold-cathode tube, the light source at this time also uses white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements. In addition, in organic light-emitting display devices, color filters are used for color adjustment and the like.

In recent years, there is a trend for image display devices to save power. In order to improve the utilization efficiency of the backlight, color filters are particularly required to increase the brightness. Especially in terms of mobile displays (mobile phones, smart phones, tablet PCs), it will become a major issue.

Here, the color filter generally has: a substrate; a coloring layer formed on the substrate and composed of coloring patterns of three primary colors of red, green, and blue; and a light-shielding portion formed on the substrate to distinguish each coloring pattern.

The method of forming the colored layer of a color filter is, for example, in a color material dispersion in which a color material is dispersed using a dispersant, etc., a binder resin, a photopolymerizable compound, and a photoinitiator are added to form a colored resin composition, After coating on the glass substrate and drying, exposure is performed using a photomask, and development is performed 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.

The color filter is under the foreseeable high-brightness requirement. Compared with the prior art, by increasing the color material concentration of the color layer of the color filter, the components necessary for photopolymerization are relatively reduced, and patterning is difficult. In addition, in order to increase the productivity of color filters, it is required to reduce the cumulative exposure required for patterning, but how to ensure the curability necessary for patterning has become a major issue.

In order to obtain a method capable of achieving a high-sensitivity colored resin composition, it has been proposed to use an oxime ester-based photoinitiator. For example, Patent Document 1 proposes an oxime ester compound containing a carbazole skeleton and having a specific structure. In addition, Patent Document 2 proposes an oxime ester sulfonate compound having a specific structure in which an oxime ester group is not bonded to a carbonyl group on the sulfonium skeleton. In addition, Patent Document 3 proposes an oxime ester compound containing a diphenyl sulfide skeleton or a carbazole skeleton, and the oxime ester group has a specific substituent containing a cycloalkyl group.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 3992725

Patent Document 2: Japanese Patent Special Form 2015-523318

Patent Document 3: Chinese Patent Application Publication No. 103293855 Specification

However, the conventional colored resin composition using an oxime ester-based photoinitiator tends to have insufficient brightness. In particular, the conventionally-known high-sensitivity oxime ester-based photoinitiator has a tendency to decrease the brightness easily. On the other hand, the oxime ester-based photoinitiator, which tends to show good brightness, has low sensitivity. The oxime ester-based photoinitiator has a see-saw relationship between sensitivity and brightness. Therefore, there is a demand for a colored resin composition that can achieve high sensitivity and can form a higher-brightness colored layer.

The present invention has been completed in view of the foregoing facts, and its object is to provide a photosensitive colored resin composition for color filters that can form a colored layer with enhanced brightness and has good sensitivity, and has photosensitivity for use of the color filter A color filter with a colored layer formed by a colored resin composition, and a display device using the color filter.

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

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

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

Furthermore, the present invention provides a display device equipped with the above-mentioned color filter of the present invention.

According to the present invention, it is possible to provide: a photosensitive colored resin composition for color filters that can form a colored layer with increased brightness and has good sensitivity, and has a colored layer formed by using the photosensitive colored resin composition for color filters The color filter, and the display device using the color filter.

1‧‧‧Substrate

2‧‧‧Shading part

3‧‧‧Coloring layer

10‧‧‧Color filter

20‧‧‧Reverse substrate

30‧‧‧Liquid crystal layer

40‧‧‧LCD device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧hole injection layer

73‧‧‧Electric tunnel transport layer

74‧‧‧Light-emitting layer

75‧‧‧Electron injection layer

76‧‧‧Cathode

80‧‧‧Organic luminous body

100‧‧‧Organic light emitting display device

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

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

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

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

In addition, in the present invention, the optical system covers electromagnetic waves and radiation having wavelengths in the visible and non-visible regions, and the radiation system covers, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less.

In the present invention, the term "(meth)acryl" refers to an acrylic group and a methacryl group, and the term "(meth)acrylate" refers to an acrylate and a methacrylate, respectively.

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

I. Photosensitive colored resin composition for color filters

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

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

The photosensitive colored resin composition for color filters of the present invention uses the oxime ester compound represented by the general formula (1) as a photoinitiator to form a colored layer with enhanced brightness and good sensitivity. In addition, the photosensitive colored resin composition system for color filters of the present invention has the advantages of suppressing the occurrence of development residues and, when the colored layer is patterned, the desired minute holes can be easily formed in the colored layer at the same time.

The photosensitive colored resin composition for a color filter of the present invention uses the oxime ester compound represented by the general formula (1) as a photoinitiator to exert the above-mentioned effect, although it is not clear, but it can be estimated as follows.

The brightness of the colored layer decreases. Among them, the coloring phenomenon caused by the reaction residue of the photoinitiator may be one of the causes. The conventional oxime ester-based initiators having high sensitivity but insufficient brightness of the colored layer are presumed to have, for example, a carbazole skeleton, etc., and have a structure that easily causes coloration of the reaction residue of the photoinitiator. In contrast, the oxime ester compound represented by the above general formula (1) used in the present invention has a structure that is unlikely to be a cause of coloration of the reaction residue and has a high transmittance, so that the coloration layer caused by the reaction residue can be suppressed As a result of coloring, it can be considered that a colored layer with enhanced brightness can be formed.

Furthermore, the oxime ester compound represented by the above general formula (1) used in the present invention has a chlorophyll skeleton and has an oxime ester group via a carbonyl group, so the conjugated system of this structure will not adversely affect the brightness, by The structure that enhances the absorption intensity during exposure, it is estimated that the sensitivity is good. In addition, the oxime ester compound represented by the above general formula (1) used in the present invention is a photopolymerization initiator that generates methyl radicals, which generates a larger number of carbon alkane radicals or aromatic radicals. The photopolymerization initiator is considered to have good sensitivity due to the rapid movement of free radicals.

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

Furthermore, the photosensitive colored resin composition system for a color filter of the present invention can easily form required micropores in the colored layer at the same time when the colored layer is patterned. When a higher-sensitivity photoinitiator is used to form a colored layer, after free radicals are generated, the free radicals will move to the unexposed part, resulting in the exposed part still retains the shape of an unexposed part and is not exposed It is more difficult to form a non-trembling state in the peripheral part. Therefore, in the conventional photosensitive resin composition, if a high-sensitivity photoinitiator capable of forming a fine-line pattern is used, even if the linearity of the fine-line pattern is good, it is quite difficult to form minute holes. In addition, as in Comparative Example 2 described later, if a low-sensitivity photoinitiator is used, even if micropores can be formed, there is a problem that the residual film rate decreases. 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). Especially by adjusting the content of the photoinitiator and the content of the antioxidant used in combination, it is easier to form fine-shaped micropores. The photosensitive colored resin composition for a color filter of the present invention can easily form required micropores on the colored layer, and is therefore also suitable for forming a reflective color filter on a TFT substrate, for example. Layer, and at the same time form the purpose of conducting general-purpose through holes in the colored layer.

Furthermore, the oxime ester compound represented by the above general formula (1) used in the present invention has an oxime ester group via a carbonyl group on the stilbene skeleton, thereby having an oxime ester bonded to the stilbene skeleton without a carbonyl group. Under the oxime ester compound of the base structure, because the crystallinity is reduced, the solvent solubility and solvent re-solubility are improved, and the compatibility with other components becomes good. By using a photoinitiator with improved solvent solubility, solvent re-solubility, and compatibility with other components, the linearity of the fine line pattern can be improved, or the phenomenon of micro-hole shaking can be easily suppressed.

Furthermore, the oxime ester compound represented by the above general formula (1) has a high thermal decomposition temperature, and thus can suppress the outgassing when the coating film is heated. Therefore, the reliability of the photoresist is high. For example, when other layers such as a conductive film are further laminated on the coating film, the laminated layer can be prevented from being damaged due to outgassing.

The photosensitive colored resin composition for color filters of the present invention contains: color materials, alkali-soluble resins, photopolymerizable compounds, photoinitiators, and solvents, and may be used within a range that does not impair the effects of the present invention. It further contains other ingredients.

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

[Photoinitiator] <Oxime ester compound represented by general formula (1)>

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

In the above general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group. From the viewpoint of solvent solubility and compatibility with other components, R ^a and R ^{b are} preferably each independently an alkyl group. The alkyl group can be linear, branched, cyclic, or any of these combined alkyl groups. Examples of the alkyl group include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, isopentyl, n-hexyl, cyclopentyl, methyl ring Pentyl, cyclopentylmethyl, cyclohexyl, etc., of which alkyl groups with 2 to 6 carbon atoms are preferred, alkyl groups with 2 to 4 carbon atoms are more preferred, and straight-chain alkanes with 2 to 4 carbon atoms are particularly preferred. base.

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

基、異

基、二環戊基、金剛烷基、低級烷基取代金剛烷基等。上述烯基係可為直鏈狀、分支狀、環狀中之任一者，可舉例如：乙烯基、烯丙基、丙烯基等。上述芳基係可舉例如：苯基、聯苯、萘基、甲苯基、二甲苯基等。上述芳烷基係可舉例如：苄基、苯乙基、萘甲基、萘乙基等。R^c的烴基，尤其較佳係碳數1~14之烴基，更佳係碳數1~10之烷基、碳數7~8之芳烷基及碳數6~10之芳基，特佳係碳數1~10之烷基。又，當在著色層中形成微小孔時，從提升微小孔形狀的觀點而言，R^c的烴基較佳係碳數達2以上。又，從溶劑溶解性、相溶性的觀點而言，R^c的烴基較佳係含有環戊基甲 基、環己基甲基等環狀及直鏈狀烷基的構造。 Examples of the hydrocarbon group of R ^c include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. The above-mentioned alkyl group may be any of linear, branched, and cyclic, and may be a combination of linear and cyclic. Examples of the above-mentioned alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, and cyclopentyl. , Cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylethyl,

Base, different

Group, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc. The above-mentioned alkenyl group may be any of linear, branched, and cyclic, and examples thereof include vinyl, allyl, and propenyl. Examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl and the like. Examples of the aralkyl group include benzyl, phenethyl, naphthylmethyl, and naphthylethyl. The hydrocarbon group of R ^c is particularly preferably a hydrocarbon group with 1 to 14 carbons, more preferably an alkyl group with 1 to 10 carbons, an aralkyl group with 7 to 8 carbons, and an aryl group with 6 to 10 carbons. It is an alkyl group with 1 to 10 carbon atoms. In addition, when forming micropores in the colored layer, from the viewpoint of improving the shape of the micropores, ^{the hydrocarbon group of R c} preferably has a carbon number of 2 or more. In addition, from the viewpoint of solvent solubility and compatibility, ^{the hydrocarbon group of R c} preferably has a structure containing cyclic and linear alkyl groups such as cyclopentylmethyl and cyclohexylmethyl.

Furthermore, in the above-mentioned R ^c , the solvent solubility and compatibility can be improved by the above-mentioned hydrocarbon group containing the above-mentioned divalent linking group. The above-mentioned divalent linking group is particularly preferably a sulfide bond (-S-) or an ether bond (-O-) from the viewpoint of improving solvent solubility. In the above R ^c , when the hydrocarbyl group contains the divalent linking group, the hydrocarbyl group may be bonded to the carbon atom of the oxime ester group via the divalent linking group, and the carbon atom of the hydrocarbyl group may be directly bonded to The carbon atom of the oxime ester group. In the above R ^c , when the hydrocarbyl group contains the divalent linking group, and the carbon atom of the hydrocarbyl group is directly bonded to the carbon atom of the oxime ester group, for example, the R ^c system uses the divalent linking group between the hydrocarbyl groups. The condition of the base of the connection base phase. The groups in which the hydrocarbon groups are bonded to each other by the above-mentioned divalent linking group include, for example, alkylthioalkyl groups such as methylthiomethyl, and sulfide bond (-S-)-containing structures such as arthioalkyl groups; Structures containing ether linkage (-O-) such as oxymethyl, methoxycyclohexyl, alkoxyalkyl, aryloxyalkyl, etc.; The structure of carbonyl bond (-CO-), etc.

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

The above R ^d may also contain at least one hydrocarbon group selected from oxygen atoms and sulfur atoms. Examples include the hydrocarbon groups described in R ^c , the hydrocarbon groups described in R ^c , and further include ether linkages. A group of at least one linking group selected from oxygen atom-containing linking groups such as (-O-) and carbonyl bond (-CO-) and sulfur atom-containing linking groups such as thioether bond (-S-), among which preferred It is a hydrocarbon group with 1 to 14 carbons, more preferably an alkyl group with 1 to 10 carbons, an aralkyl group with 7 to 8 carbons, and an aryl group with 6 to 10 carbons. Especially preferred are aromatics with 6 to 10 carbons. base.

Furthermore, a heterocyclic group which does not contain a nitrogen atom but contains at least one selected from an oxygen atom and a sulfur atom, and its heterocyclic ring system includes, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, Thienothiophene ring, fluorinated furan ring, thienofuran ring, etc. The hydrocarbon group or the heterocyclic group of the R ^d preferably has 1 to 10 carbon atoms from the viewpoint of developability.

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

, R ^e hydrocarbon-based carbon number above general formula (1) of 1 to 10. The hydrocarbon group having 1 to 10 carbon atoms includes, for example, those having 1 to 10 carbon atoms in the hydrocarbon group described in R ^c. In particular, from the viewpoint to enhance the sensitivity in terms of the preferred system R ^e alkyl having 1 to 10 carbon atoms and the aryl group of 6 to 10, more preferably based carbon number of an alkyl group having 1 to 6, particularly preferably based carbon The number of alkyl groups from 1 to 4 is the best methyl group.

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

The above general formula (1) oxime ester-based compound can be exemplified as: R ^a and R ^b are alkyl groups having 1 to 4 carbon atoms of, R ^C is alkyl of 1 to 4, Z is a hydrogen atom, R compound having a carbon number of an alkyl group having 1 to 4 ^e is a; R ^a and R ^b are alkyl groups having 1 to 6 carbon atoms of, R ^c is a linear alkyl group with a combination of a cyclic alkyl group having 4 to 10 carbon atoms the alkyl group, Z is a hydrogen atom, an alkyl compound having a carbon number of 1 to 4 is R ^e; R ^a and R ^b are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms of, R ^c is a 1 to 4 carbon atoms The alkyl group, Z is -(C=O)R ^d , R ^d is an aryl group with 6 to 10 ^{carbons, and R e} is an alkyl group with 1 to 4 carbons, etc., but they are not limited to these.

The more preferable oxime ester compound represented by the above general formula (1) may include at least one selected from the following compounds (1-1) to (1-4): [化3]

The oxime ester compound represented by the above general formula (1) is based on, for example, Japanese Patent Special Publication No. 2012-526185, which replaces diphenyl sulfide or its derivatives, and uses quince or its derivatives instead, by matching the materials used It can be synthesized by appropriately selecting solvent, reaction temperature, reaction time, purification method, etc.

In the colored resin composition of the present invention, from the viewpoints that it can form a colored layer with improved brightness, has good sensitivity, and can easily adjust the line width during pattern formation, it is preferable that the above-mentioned photoinitiator contains two or more types. An oxime ester compound with a carbazole skeleton. The oxime ester compound without a carbazole skeleton is less likely to cause the coloring of the reaction residue, and therefore can suppress the decrease in the brightness of the colored layer. In addition, by appropriately selecting and combining two or more types of oxime ester compounds containing the oxime ester compound represented by the above general formula (1) and having different sensitivities, the line width during pattern formation can be adjusted while maintaining a good sensitivity. When the coloring resin composition of the present invention contains two or more types of oxime ester compounds without a carbazole skeleton, at least one type of oxime ester compound represented by the above general formula (1) may be contained, or two types may be contained. The above oxime ester compound represented by the above general formula (1) can also be combined to contain the oxime ester compound represented by the above general formula (1), and other oxime ester compounds different from the above general formula (1) without carbazole The backbone of the oxime ester compound.

Among them, from the viewpoint of not causing a significant decrease in brightness, developability, and sensitivity, and being able to easily improve the shape of the micropores, it is preferable to use the oxime ester compound represented by the above general formula (1) in combination with a diphenyl sulfide skeleton Oxime ester compound.

(一般式(2)中，R^c'及R^f係各自獨立之亦可含有從硫醚鍵(-S-)、醚鍵(-O-)及羰鍵(-CO-)中選擇之至少1種2價連接基的碳數1~14之烴基；Z¹係氫原子、硝基或-(C=O)R^d'；R^d'係可亦含有從氧原子及硫原子中選擇之至少1種的烴基、或未含氮原子但含有從氧原子及硫原子中選擇之至少1種的雜環基。) Preferably, the oxime ester compound having a diphenyl sulfide skeleton can use the oxime ester compound represented by the following general formula (2): [formation 4] general formula (2)

(In general formula (2), R ^c'and R ^f are independent of each other and may contain at least one selected from thioether bond (-S-), ether bond (-O-) and carbonyl bond (-CO-) One type of bivalent linking group is a hydrocarbon group with 1 to 14 carbon ^{atoms; Z 1} is a hydrogen atom, a nitro group or -(C=O)R ^d' ; R ^d' may also contain an oxygen atom and a sulfur atom At least one type of hydrocarbon group, or a heterocyclic group that does not contain a nitrogen atom but contains at least one selected from an oxygen atom and a sulfur atom.)

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

^{The Z 1} of the above general formula (2) is a hydrogen atom, a nitro group, or -(C=O)R ^d' ; the R ^d' system may also contain at least one hydrocarbon group selected from an oxygen atom and a sulfur atom, or not However, selection of a nitrogen atom containing heterocyclic group is at least one selected from oxygen atom and sulfur atom; the R ^{d 'and} R lines can be exemplified as the above general formula (1) ^d of the same person. Among the above-mentioned Z ¹ , from the viewpoint of developability and brightness, a hydrogen atom or -(C=O)R ^d'is preferable, and from the viewpoint of brightness, a hydrogen atom is more preferable.

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

The above general formula (2) can be exemplified oxime ester-based compounds such as: R ^{c 'is} a linear alkyl group with a carbon number cyclic alkyl group having 6 to 10 in combination of; Z ¹ is a hydrogen atom, R ^f is compound having a carbon number of an alkyl group having 1 to 4; R ^{c 'is} a linear alkyl group having a carbon number and combination of cyclic alkyl group of 6 to 10, Z ¹ is ^{- (C = O) R d} ', the R ^d' is a heterocyclic group containing no nitrogen atom but a sulfur atom, a compound in which R ^f is an alkyl group having 1 to 4 carbon atoms, etc., but it is not limited to these.

More preferable oxime ester compounds represented by the above general formula (2) include at least one selected from the following compounds (2-1) to (2-2), for example.

[化5]

The oxime ester compound represented by the above general formula (2) can be synthesized by referring to Japanese Patent Publication No. 2012-526185, for example.

In the photosensitive colored resin composition for color filters of the present invention, the photoinitiator may be further used in combination with other photoinitiators other than the above-mentioned oxime ester compound. In addition, 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>

系光起始劑、醯化膦氧化物系光起始劑及巰系鏈轉移劑等。 Other photoinitiators include, for example, other oxime ester photoinitiators and α-amine ketone photoinitiators, which are different from the oxime ester compound represented by the above general formula (1) and do not have a carbazole skeleton. Initiator, biimidazole-based photoinitiator, oxysulfur

It is a photoinitiator, phosphine oxide photoinitiator, sulfhydryl chain transfer agent, etc.

系光起始劑、醯化膦氧化物系光起始劑與巰系鏈轉移劑中選擇之至少1種。其中，就從形成微小孔時，抑制孔端部顫抖，俾輕易形成良好尺寸精度微小孔的觀點而言，最好更進一步組合使用醯化膦氧化物系光起始劑。因為醯化膦氧化物系光起始劑的熱分解溫度較高其他起始劑，因而不易因預烘烤時的加熱而引發副反應，藉而可認為能抑制顫抖。 In particular, from the viewpoint of improving the linearity when forming thin line patterns in the increased brightness state, or the ability to form thin line patterns such as the design mask line width, and the viewpoint of improving the shape of the micro holes, the above general formula ( 1) The oxime ester compound shown is preferably a further combination of α-amine ketone-based photoinitiator, diimidazole-based photoinitiator, oxysulfur

At least one selected from photoinitiator, phosphine oxide photoinitiator and sulfhydryl chain transfer agent. Among them, from the viewpoint of suppressing the shaking of the hole ends when forming the micropores and facilitating the formation of fine pores with good dimensional accuracy, it is preferable to further use the phosphine oxide-based photoinitiator in combination. Since the thermal decomposition temperature of the phosphine oxide-based photoinitiator is higher than other initiators, it is not easy to cause side reactions due to heating during pre-baking, which can be considered to suppress shaking.

The so-called "improving linearity" means that after the coloring composition is applied, the end of the colored layer formed in the development step has less unevenness and becomes linear or slightly linear. In addition, the so-called "tremor" refers to the inconsistency of straight lines or curves at the end of the pattern, resulting in poor dimensional accuracy.

系光起始劑、醯化膦氧化物系光起始劑與巰系鏈轉移劑中選擇之至少1種、與上述具二苯硫醚骨架的肟酯化合物，更佳係組合使用後述抗氧化劑。 Furthermore, from the viewpoint of improving the shape of the micropores and suppressing tremor, the oxime ester compound represented by the above general formula (1) is preferably used in combination with a photoinitiator from an α-amine ketone-based photoinitiator and a diimidazole-based photoinitiator. Oxysulfur

At least one selected from a photoinitiator, a phosphine oxide photoinitiator, and a mercapto-based chain transfer agent, and the above-mentioned oxime ester compound with a diphenyl sulfide skeleton, more preferably a combination of the antioxidant described later .

Since the α-amine ketone photoinitiator has the property of hardening the middle from the surface of the coating film, it is easy to inhibit the deep hardening of the coating film. Therefore, if it is combined with the oxime ester compound represented by the above general formula (1), the coating can be improved. The tendency of deep film hardening is better.

啉基丙烷-1-酮(例如IRGACURE 907、BASF公司製)、2-苄基-2-(二甲胺基)-1-(4-

啉基苯基)-1-丁酮(例如IRGACURE 369、BASF公司製)、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮(IRGACURE 379EG、BASF公司製)等。 Examples of α-aminoketone-based photoinitiator systems include: 2-methyl-1-(4-methylthiophenyl)-2-

Alkylpropan-1-one (e.g. IRGACURE 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-

(Alolinylphenyl)-1-butanone (e.g. IRGACURE 369, manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( 4-

(Alkolinyl)phenyl]-1-butanone (IRGACURE 379EG, manufactured by BASF Corporation) and the like.

啉基丙烷-1-酮及2-苄基-2-(二甲胺基)-1-(4-

啉基苯基)-1-丁酮；從抑制微小孔顫抖的觀點而言，更佳係2-甲基-1-(4-甲基硫苯基)-2-

啉基丙烷-1-酮。 The α-aminoketone-based photoinitiator can be used alone or in combination of two or more. Among them, from the viewpoint of increasing the residual film rate, 2-methyl-1-(4-methylthiophenyl) is preferred. )-2-

Linylpropane-1-one and 2-benzyl-2-(dimethylamino)-1-(4-

Linylphenyl)-1-butanone; from the viewpoint of suppressing the shaking of micropores, 2-methyl-1-(4-methylthiophenyl)-2-

Altopropan-1-one.

The diimidazole-based photoinitiator has the property of hardening the deep part of the coating film and easily inhibits the surface hardening of the coating film. When combined with the oxime ester compound represented by the above general formula (1), it has a high tendency to improve the surface hardenability of the coating film. From a viewpoint, it is better.

Examples of diimidazole-based photoinitiators include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1, 2'-diimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetra(4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4-dichlorobenzene Yl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 ,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-di Imidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2, 4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole and the like.

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

系光起始劑係可舉例如：2,4-異丙基氧硫

、2,4-二乙基氧硫

、1-氯-4-丙氧基氧硫

、2,4-二氯氧硫

等。 Oxygen Sulfur

Examples of photoinitiators include: 2,4-isopropyloxysulfur

, 2,4-Diethyloxysulfur

, 1-Chloro-4-propoxysulfur

, 2,4-Dichlorosulfuryl

Wait.

系光起始劑係可單獨使用、或組合使用2種以上，其中，從提升自由基生成性轉移的觀點而言，較佳係使用2,4-異丙基氧硫

、2,4-二乙基氧硫

。 Oxygen Sulfur

The photoinitiator can be used alone or in combination of two or more types. Among them, from the viewpoint of enhancing the transfer of free radicals, it is preferable to use 2,4-isopropyloxysulfur.

, 2,4-Diethyloxysulfur

.

Although the phosphine oxide-based photoinitiator has the property of less yellowing due to heat, and is suitable for increasing the brightness, it generally has low sensitivity and insufficient curability. However, if it is combined with the oxime ester compound represented by the general formula (1) above, the overall coating film curability will be improved, and when the micropores are formed, the shaking of the hole ends can be suppressed, so that the micropores with good dimensional accuracy can be easily formed. Hole is better in this regard.

Examples of the phosphine oxide-based photoinitiator system include: benzyl-diphenylphosphine oxide, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, 2,3, 5,6-Tetramethylbenzyl-diphenylphosphine oxide, 3,4-dimethylbenzyl-diphenylphosphine oxide, 2,4,6-trimethylbenzyl- Phenylethoxy phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4, 4-trimethyl-pentyl phosphine oxide, bis(2,6-dimethylbenzyl)-ethyl phosphine oxide and the like.

The phosphine oxide-based photoinitiator system can be used singly or in combination of two or more. From the viewpoint of improving the hardenability of the coating film, it is preferable to use bis(2,4,6-trimethylbenzyl). (Phenyl)-phenylphosphine oxide.

The sulfhydryl chain transfer agent has the property of accepting free radicals from slow-reacting free radicals and accelerating the reaction. In particular, from the viewpoint of a high tendency to increase the reaction speed, it is preferable to use a diimidazole-based photoinitiator in combination.

唑、 2-巰基苯并咪唑、2-巰基-5-甲氧基苯并噻唑、2-巰基-5-甲氧基苯并咪唑、3-巰基丙酸、3-巰基丙酸甲酯、3-巰基丙酸乙酯、3-巰基丙酸辛酯、1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、季戊四醇四(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)及四乙二醇雙(3-巰基丙酸酯)等。 The sulfhydryl chain transfer agent system can include, for example: 2-mercaptobenzothiazole, 2-mercaptobenzo

Azole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl ester, 3 -Ethyl mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1 ,3,5-three

-2,4,6(1H,3H,5H)-triketone, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropane) Acid ester), dipentaerythritol hexa(3-mercaptopropionate) and tetraethylene glycol bis(3-mercaptopropionate).

The mercapto-based chain transfer agent may be used alone or in combination of two or more types. Among them, from the viewpoint of increasing the reaction rate, it is preferable to use 2-mercaptobenzothiazole.

The total content of the photoinitiator used in the photosensitive colored resin composition for the color filter of the present invention is not limited, provided that the effect of the present invention is not impaired. The total solid content of the photosensitive colored resin composition is preferably in the range of 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less. If the content exceeds the above lower limit, it will fully promote photohardening and inhibit the elution of exposed parts during development; on the other hand, if the content is below the above upper limit, the yellowing of the obtained colored layer can be inhibited from increasing, and Causes a decrease in brightness.

In addition, the term "solid content" refers to everything 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 relative to the total solid content of the photosensitive colored resin composition for color filters. It is preferably in the range of 0.1% by mass or more and 8.0% by mass or less, and more preferably 0.5% by mass or more and 6.0% by mass or less. If the content is above the above lower limit, it will fully promote photohardening and inhibit the elution of the exposed part during development; on the other hand, if the content is below the above upper limit, the yellowing of the obtained colored layer can be inhibited from increasing, and Causes a decrease in brightness.

Furthermore, when the photoinitiator contains two or more types of oxime ester compounds that do not have a carbazole skeleton, the photosensitive colored resin composition for color filters of the present invention contains the oxime ester compound represented by the above general formula (1) The total content of the two or more oxime ester compounds without a carbazole skeleton is compared to the solid state of the photosensitive colored resin composition for color filters from the viewpoint of fully exerting the effect of using these photoinitiators together The total amount is preferably 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less.

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

When the photoinitiator used in the present invention is in the oxime ester compound represented by the above general formula (1), and the above oxime ester compound having a diphenyl sulfide skeleton is combined, the oxime ester compound represented by the above general formula (1) , And the ratio of the above-mentioned oxime ester compound with diphenyl sulfide skeleton, from the viewpoint of brightness and sensitivity, with respect to 100 parts by mass of the oxime ester compound represented by the above general formula (1), the above-mentioned diphenyl sulfide skeleton The oxime ester compound is preferably 10 parts by mass or more and 150 parts by mass or less, more preferably 15 parts by mass or more and 120 parts by mass or less. From the viewpoint of easy formation of micropores, relative to 100 parts by mass of the oxime ester compound represented by the general formula (1), 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.

Furthermore, in the photosensitive colored resin composition for color filters of the present invention, when the photoinitiator further contains a photoinitiator other than the above, the oxime ester compound represented by the above general formula (1) and the above The total content of the oxime ester compound having a diphenyl sulfide skeleton accounts for 100 parts by mass of the total photoinitiator used in the present invention, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, The best series is more than 50 parts by mass.

On the other hand, from the viewpoint of fully exerting the effect of combining with other photoinitiators except 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 , In the total 100 parts by mass of the photoinitiator used in the present invention, preferably 95 parts by mass or less, more preferably 85 parts by mass or less.

系光起始劑、醯化膦氧化物系光起始劑與巰系鏈轉移劑中選擇之至少1種的情況，從充分發揮與該等光起始劑併用效果的觀點而言，相對於彩色濾光片用感光性著色樹脂組成物的固形份總量，該等的合計含有量較佳係0.1質量%以上且4.0質量%以下、更佳係0.5質量%以上且2.0質量%以下範圍內。 When the photoinitiator used in the present invention further contains a photoinitiator from α-amine ketone, diimidazole photoinitiator,

In the case of selecting at least one of a photoinitiator, a phosphine oxide photoinitiator, and a mercapto-based chain transfer agent, from the viewpoint of fully exerting the effect of using these photoinitiators in combination, relative to The total solid content of the photosensitive colored resin composition for color filters, the total content of these is preferably 0.1% by mass or more and 4.0% by mass or less, more preferably 0.5% by mass or more and 2.0% by mass or less .

[Color material]

In the present invention, the color material can be used as long as it can develop the desired color when forming the coloring layer of the color filter. The rest is not particularly limited, and two or more of various organic pigments, inorganic pigments, Dispersible dyes and dyes. Among them, organic pigments are preferred because they have high color development and high heat resistance. Organic pigments are compounds that are classified as pigments in the Pigment Index (C.I.; published by The Society of Dyers and Colourists), and specific ones include, for example, those assigned with the following Pigment Index (C.I.) numbers.

In addition, when the paint index name is described below, if only the number is different among the listed paint index names, there may be cases where only the number is listed.

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

Furthermore, specific examples of the above-mentioned inorganic pigments include: titanium oxide, barium sulfate, calcium carbonate, zinc bloom, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, Ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, etc.

For example, when the photosensitive colored resin composition for a color filter of the present invention is used on the substrate of a color filter to form a pattern of a light-shielding layer, a highly light-shielding black pigment is blended into the ink. For high light-shielding black pigments, for example, inorganic pigments such as carbon black and ferroferric oxide; or organic pigments such as cyanine black can be used.

Examples of the above-mentioned dispersible dyes include: dyes that are insoluble in solvents by imparting various substituents to the dyes; dyes that are dispersible by using a solvent with low solubility in combination; Dyes and counter ions form a lake color material that does not melt (lake). By using such a dispersible dye and dispersant, the dispersibility and dispersion stability of the dye can be improved.

In addition, the index indicates that if the amount of the dye dissolved in 10 g of solvent (or mixed solvent) is less than 100 mg, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

The above-mentioned dye system can be appropriately selected from conventionally known dyes. Examples of such dyes include: azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, anthocyanin dyes, naphthoquinone dyes, quinoneimine dyes, Methyl dyes, phthalocyanine dyes, etc. Specific systems include, for example: CI Solvent Yellow 4, 14, 15, 24, 82, 88, 94, 98, 162, 179; CI Solvent Red 45, 49; CI Solvent Orange 2, 7, 11, 15, 26, 56 ; CI Solvent Blue 35, 37, 59, 67; CI Acid Red 50, 52, 289; CI Acid Violet 9, 30; CI Acid Blue 19 and so on.

When forming the blue colored layer, from the viewpoint of high brightness, at least one of triarylmethane dyes, dibenzopyran dyes, and anthocyanin dyes is particularly preferred, and it has high heat resistance. From the viewpoint of, preferably at least one selected from triarylmethane-based dyes and dibenzopyran-based dyes.

In the present invention, from the viewpoint of enhancing the brightness of the color filter, it is preferable to contain a lake color material with triarylmethane-based dyes, and it is more preferable to contain triarylmethane-based basic dyes and polyoxometallic acids. Salt anion.

In the present invention, the above-mentioned lake color material is preferably a color material represented by the following general formula (i) from the viewpoint of excellent heat resistance and light resistance and high brightness of the color filter, forming a molecular association The state is preferable from the viewpoint of exhibiting more excellent heat resistance.

[化6] General formula (i)

(In the general formula (i), A series represents an a-valent organic group that does not have a π bond on the carbon atom directly bonded to N, and this organic group represents a saturated aliphatic hydrocarbon group at least at the end directly bonded to N The aliphatic hydrocarbon group or the aromatic group with the aliphatic hydrocarbon group may also contain O, S, and N in the carbon chain. B ^c- represents a c-valent polyoxometalate anion. R ⁱ ~R ^v represent each An alkyl group which is independently a hydrogen atom, which may have a substituent, or an aryl group which may have a substituent, may be formed by ^{bonding R ii} and R ⁱⁱⁱ , and R ^iv and R ^v to form a ring structure. Ar ¹ may also be represented by the system A bivalent aromatic group having a substituent. The plural R ⁱ to R ^v and Ar ¹ may be the same or different.

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

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

In the above general formula (i), the carbon atom directly bonded to N (nitrogen atom) is an a-valent organic group that does not have a π bond. The organic group means that it has saturated fat at least at the end directly bonded to N The aliphatic hydrocarbon group of the group hydrocarbon group or the aromatic group having the aliphatic hydrocarbon group may contain O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. Because the carbon atom directly bonded to N does not have a π bond, the color characteristics such as hue and transmittance of the cationic coloring part will not be affected by the linking group A and other coloring parts, and can be maintained with The same color as the monomer.

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

Furthermore, in A, the above-mentioned aromatic group having an aliphatic hydrocarbon group includes, for example, a monocyclic or polycyclic aromatic group containing an aliphatic hydrocarbon group (which has a saturated aliphatic hydrocarbon group at least at the end directly bonded to N) , May have a substituent, and may be a heterocyclic ring containing O, S, and N.

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

烷、雙環[2,2,2]辛烷、二環戊二烯、金剛烷等。有橋脂環式烴基中較佳係降

烷。又，芳香族基係可例如含有苯環、萘環的基，其中較佳係含苯環的基。 From the standpoint of skeletal fastness, the cycloaliphatic hydrocarbon group is preferably a bridged alicyclic hydrocarbon group. The so-called "bridged alicyclic hydrocarbon group" refers to a polycyclic aliphatic hydrocarbon group with a bridge structure in the aliphatic ring and a polycyclic structure, such as:

Alkanes, bicyclo[2,2,2]octane, dicyclopentadiene, adamantane, etc. The preferred series of bridged alicyclic hydrocarbon groups

alkyl. In addition, the aromatic group may include, for example, a group containing a benzene ring and a naphthalene ring, and among them, a group containing a benzene ring is preferred.

From the viewpoint of the ease of obtaining raw materials, A is preferably more than or equal to divalent and less than or equal to tetravalent, more preferably more than or equal to divalence and less than or equal to trivalent, and particularly preferably divalent. For example, in the case of an A-based divalent organic group, for example, a linear, branched, or cyclic alkylene group having 1 or more and 20 or less carbon atoms; Aromatic groups substituted with alkylene groups of 20 or less.

The alkyl group of R ⁱ to R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, etc., and a linear or branched alkyl group having 1 or more and 8 carbon atoms is particularly preferred. From the viewpoint of ease of production and raw material scheduling, it is more Preferably, it is a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Among them, ^{the alkyl group of R i} to R ^v 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 an aryl group, a halogen atom, and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group.

The aryl group of R ⁱ to R ^v is not particularly limited. For example, phenyl, naphthyl, etc. Examples of the substituent system that the aryl group may have include an alkyl group and a halogen atom.

啉環等。 The so-called "R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v are bonded to form a ring structure" means that R ⁱⁱ and R ⁱⁱⁱ , and R ^iv and R ^v form a ring structure via a nitrogen atom. The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring,

Morpholino ring and so on.

啉環。 Among them, from the viewpoint of chemical stability, R ⁱ to R ^{v are} preferably each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v phase bonds to form pyrrolidine ring, piperidine ring,

Morpholino ring.

R ⁱ ~ R ^v systems can each independently form the above-mentioned structure, but from the viewpoint of color purity, R ^{i is} preferably a hydrogen atom, and from the viewpoint of ease of manufacturing and raw material scheduling, R ⁱⁱ ~ R ^v are all the same.

唑、噻唑、咪唑、吡唑等五元雜環；吡喃、哌喃酮、吡啶、哌喃酮、噠

、嘧啶、吡

等六元雜環；苯并呋喃、噻茚、吲哚、咔唑、香豆素、苯并哌喃酮、喹啉、異喹啉、吖啶、酞

、喹唑啉、喹

啉等縮合多環式雜環。該等芳香族基亦可具有取代基。 The divalent aromatic group of Ar ^{1 is not particularly limited.} The aromatic group may be a heterocyclic group in addition to an aromatic hydrocarbon group composed of a carbocyclic ring. In addition to the benzene ring, the aromatic hydrocarbon system of the aromatic hydrocarbon group can also include, for example, naphthalene ring, tetralin ring, indene ring, stilbene ring, anthracene ring, phenanthrene ring and other condensed polycyclic aromatic hydrocarbons; biphenyl, biphenyl Chain polycyclic hydrocarbons such as triphenyl, diphenylmethane, triphenylmethane and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton such as diphenyl ether. On the other hand, the heterocyclic ring system of the heterocyclic group includes, for example, furan, thiophene, pyrrole,

Azole, thiazole, imidazole, pyrazole and other five-membered heterocycles; pyran, piperanone, pyridine, piperanone, pyranone

, Pyrimidine, pyridine

Six-membered heterocycles; benzofuran, thiaindene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, phthalein

, Quinazoline, quine

Condensation of polycyclic heterocycles with morpholines and the like. These aromatic groups may have a substituent.

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

Ar ^{1 is} preferably an aromatic group having 6 or more and 20 or less carbon atoms, more preferably an aromatic group composed of a condensed polycyclic carbocyclic ring having 10 or more and 14 or less carbon atoms. Among them, phenylene and naphthylene are more preferred from the viewpoint of simple structure and inexpensive raw materials.

The plural R ⁱ to R ^v and Ar ^{1 in} 1 molecule may be the same or different. When the plural R ⁱ ~R ^v and Ar ¹ are respectively the same, because the color development part is the same color, it can show the same color as the monomer of the color development part. From the viewpoint of color purity, the system is relatively high. good. On the other hand, when ^{at least one of R i} to R ^v and Ar ¹ is a different substituent, the color mixed with multiple monomers can be reproduced, and the desired color can be adjusted.

^{The anion (B c-} ) of the color material represented by the above general formula (i) is a polyoxometalate anion having a valence of two or more.

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

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

The polyoxometalate anion (B ^c- ) system can use one of the above-mentioned polyoxometalate anions alone, or two or more of them in combination. When two or more types are used in combination, the tungsten in the whole polyoxometalate anion The molar ratio to molybdenum is preferably within the above range.

The color material represented by the above general formula (i) can also form a double salt further containing other cations or anions within a range that does not impair the effect of the present invention. Specific examples of such cations include, in addition to other basic dyes, organic compounds containing functional groups such as amine groups, pyridyl groups, and imidazole groups that can form salts with anions; sodium ions, potassium ions, and magnesium Metal ions such as ions, calcium ions, copper ions, and iron ions. In addition, specific examples of anions include acid dyes, but also halide ions such as fluoride ions, chloride ions, and bromide ions; inorganic acid anions. Examples of the anion system of the above-mentioned inorganic acid include anion of oxo acid such as phosphoric acid ion, sulfuric acid ion, chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), and the like.

In addition, the color material represented by the general formula (i) is prepared with reference to International Publication No. 2012/144520, for example.

Furthermore, when forming the green colored layer, it is better to use a green color material in which a yellow color material is further combined with C.I. Pigment Green 59 (PG59) and C.I. Pigment Green 58 (PG58) which are zinc phthalocyanine pigments.

The yellow color material that can be used in combination with zinc phthalocyanine pigments such as PG59 and PG58 is particularly preferably a derivative pigment of C.I. Pigment Yellow 150. The specific series of the derivative pigments of CI Pigment Yellow 150 can include, for example, the single, two, and three azo compounds of the following general formula (ii) or one of its tautomeric structures, which have at least one guest compound as the main body. And four anions, and metal Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb (particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La) Metal complex. From the viewpoint of enhancing brightness, it is preferable to use such derivative pigments of C.I. Pigment Yellow 150.

(In the above general formula (ii), R ³¹ is each independently OH, NH ₂ , NH-CN, acylated amino, alkylamino, or arylamino; R ³² is each independently -OH or- NH ₂ )

Among them, the yellow color material is from the viewpoint of enhancing brightness and enhancing contrast, and preferably contains: from the above general formula (ii) the azo compound and the tautomeric structure of the azo compound single, two, At least one anion selected from the group consisting of three and four anions, and at least two metals selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn ion.

By containing two or more kinds of metal ions, the crystal growth of the color material can be suppressed and the particle size can be achieved. Furthermore, because it is used in combination with the dispersant described below, it is atomized in the color material dispersion liquid, and it is estimated that it will be able to form an improved contrast. The coloring layer.

The acyl group of the acylated amino group in the general formula (ii) includes, for example, alkylcarbonyl, phenylcarbonyl, alkylsulfonyl, benzenesulfonyl; carbamate which can also be substituted by alkyl, phenyl or naphthyl Amino group; sulfamidine group which may be substituted by alkyl group, phenyl group or naphthyl group; guanyl group (guanyl) which may be substituted by alkyl group, phenyl group or naphthyl group, etc. The above-mentioned alkyl group preferably has 1 to 6 carbon atoms. In addition, the above-mentioned alkyl group may be substituted with halogens such as F, Cl, and Br; or -OH, -CN, -NH ₂ and/or an alkoxy group having 1 to 6 carbon atoms. In addition, the above-mentioned phenyl and naphthyl groups may also be substituted by halogens such as F, Cl, Br; -OH, -CN, -NH ₂ , -NO ₂ , alkyl groups with 1 to 6 carbons, and/or 1 to carbon atoms. Substituted by 6 alkoxy groups.

The alkyl group of the alkylamino group in general formula (ii) preferably has 1 to 6 carbon atoms. The above-mentioned alkyl groups may also be substituted by halogens such as F, Cl, and Br; -OH, -CN, -NH ₂ and/or alkoxy groups having 1 to 6 carbon atoms.

The aryl group of the arylamino group in the general formula (ii) can include, for example, phenyl, naphthyl, and these aryl groups can also be halogenated by, for example, F, Cl, Br, etc.; -OH, carbon number 1~6 Alkyl, C1-C6 alkoxy, -NH ₂ , -NO ₂ and -CN etc. are substituted.

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

In the above general formula (ii), from the hue point of view, two R ^{31 are more} preferably when both are -OH, when both are -NH-CN, or one is -OH and the other is In the case of -NH-CN, the best case is the case where both parties are -OH.

Furthermore, the azo compound represented by the above general formula (ii) and the azo compound of its tautomeric structure, from the viewpoint of hue, R ^{32 is more} preferably a case where both are -OH.

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

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

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

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

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

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

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

In the derivative pigments of CI Pigment Yellow 150, there are at least two types of metal ions. Examples include the case where at least two types of metal ions are contained in a common crystal lattice, as well as the fact that each of the other crystal lattices contains at least two metal ions. A situation in which the crystals of a metal ion are condensed. Among them, from the viewpoint of further enhancing the contrast, it is preferable that the common crystal lattice contains at least two kinds of metal ions. In addition, whether it belongs to a state in which at least two types of metal ions are contained in a common crystal lattice, or a state in which each type of metal ion is contained in each of the other lattices is crystallized and aggregated, for example, refer to Japanese Patent Laid-Open No. 2014 Bulletin No.-12838, the X-ray diffraction method can be used for proper judgment.

The average primary particle size of the color material used in the present invention is when the coloring layer of the color filter is formed, as long as it can develop the desired color, there is no particular limitation, and it depends on the type of color material used. Different, preferably in the range of 10nm-100nm, more preferably 15nm-60nm. Since the average primary particle size of the color material is within the above range, a display device equipped with a color filter manufactured by using the color material dispersion of the present invention can achieve high contrast and high quality.

The color material used in the present invention can be produced by a known method such as a recrystallization method and a solute solvent grinding method. In addition, commercially available color materials can be used after being refined.

The total content of color materials is preferably 3% to 65% by mass, and more preferably 4% to 60% by mass relative to the total solid content of the photosensitive colored resin composition for color filters Blending. If it exceeds the above lower limit, when the photosensitive colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm), the colored layer can have a sufficient color density. Moreover, if it is below the said upper limit, it will be excellent in storage stability, and can obtain the colored layer which has sufficient hardness and adhesiveness with a board|substrate. Especially when forming a coloring layer with a high color material concentration, the total content of color materials is preferably 15% to 65% by mass relative to the total solid content of the photosensitive colored resin composition for color filters. , It is better to blend in the ratio of 25% to 60% by mass.

[Alkali-soluble resin]

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

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

The preferred alkali-soluble resin of the present invention is a resin having an acidic group (usually a carboxyl group), and specific examples include acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups; Carboxyl epoxy (meth)acrylate resin, etc. Among them, particularly preferred are those having a carboxyl group in the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. The reason is that by containing a photopolymerizable functional group, the film strength of the formed cured film can be improved. Moreover, acrylic resins and epoxy acrylate resins, such as these acrylic copolymers and styrene-acrylic copolymers, may mix and use 2 or more types.

Acrylic resins such as acrylic copolymers having carboxyl structural units and styrene-acrylic copolymers having carboxyl groups include, for example, carboxyl-containing ethylenically unsaturated monomers and other monomers that can be copolymerized as necessary. A (co)polymer obtained by performing (co)polymerization by a known method.

Examples of carboxyl-containing ethylenically unsaturated monosystems include: (meth)acrylic acid, vinyl benzoate, maleic acid, monoalkyl maleate, fumaric acid, and itaconic acid , Crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, it is also possible to use monomers with hydroxyl groups such as (meth)acrylic acid-2-hydroxyethyl, and cyclic dehydrates such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride. Addition reactants; and ω-carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, as the precursor of the carboxyl group, a dehydrated substance-containing monomer such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerization, cost, solubility, glass transition temperature, and the like.

From the viewpoint of excellent adhesion of the colored layer, the alkali-soluble resin is more preferably one having a hydrocarbon ring. It is known that the alkali-soluble resin has a hydrocarbon ring which is a bulky group, and the solvent resistance of the obtained colored layer can be suppressed, and in particular, the swelling of the colored layer can be suppressed. Although the relevant effects are not yet clear, it is estimated that the large hydrocarbon ring contained in the colored layer suppresses the molecular actions in the colored layer, resulting in an increase in the strength of the coating film and suppression of swelling due to solvents.

Such a hydrocarbon ring system may include, for example, a cycloaliphatic hydrocarbon ring which may also have a substituent, an aromatic ring which may also have a substituent, and combinations of these, and the hydrocarbon ring may also have a carbonyl group, a carboxyl group, an oxycarbonyl group, Substituents such as amide group. Among them, when an aliphatic ring is contained, the heat resistance and adhesion of the colored layer can be improved, and the brightness of the obtained colored layer can be improved.

烷、三環[5.2.1.0(2,6)]癸烷(二環戊烷)、金剛烷等脂肪族烴環；苯、萘、蒽、菲、茀等芳香族環；聯苯、聯三苯、二苯基甲烷、三苯甲烷、茋等鏈狀多環；下述化學式(A)所示懸掛結構(cardo structure)等。 Specific examples of the hydrocarbon ring include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and

Alkanes, tricyclic [5.2.1.0(2,6)] decane (dicyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, sulphur and other aromatic rings; biphenyl, dicyclopentane Chain polycyclic rings such as benzene, diphenylmethane, triphenylmethane, stilbene, etc.; cardo structure shown in the following chemical formula (A), etc.

[Chemical formula 8] Chemical formula (A)

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

(In general formula (B), R ^M may be a substituted hydrocarbon ring.)

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

^{Specific examples of the hydrocarbon ring that may be substituted for R M in} the above general formula (B) are the same as the specific examples of the hydrocarbon ring described above.

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

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

The alkali-soluble resin used in the present invention can easily adjust the amount of each constituent unit and increase the amount of the constituent unit having a hydrocarbon ring so as to easily improve the function of the constituent unit. It is preferable to use a resin having a carboxyl group The above-mentioned acrylic copolymer having a structural unit of a hydrocarbon ring other than the structural unit.

The carboxyl structural unit and the above-mentioned hydrocarbon-ring acrylic copolymer can be prepared by using the above-mentioned "other monomers capable of copolymerization" such as ethylenically unsaturated monomers having a hydrocarbon ring.

酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯等，從即便經加熱處理後，仍可維持經顯影後著色層截面形狀效果較大的觀點而言，較佳係(甲基)丙烯酸環己酯、(甲基)丙烯酸雙環戊酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸苄酯、苯乙烯，更佳係苯乙烯。 The ethylenically unsaturated monomer having a hydrocarbon ring used in combination with the oxime ester compound represented by the above general formula (1) includes, for example, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, ( Adamantyl meth)acrylate, isopropyl (meth)acrylate

Ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., are more effective in maintaining the cross-sectional shape of the colored layer after development even after heat treatment. Preferred are cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, styrene, and more preferably styrene.

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

The alkali-soluble resin used in the present invention preferably has an ethylenic double bond in the side chain. When it has an ethylenic double bond, the alkali-soluble resin and the alkali-soluble resin and the photopolymerizable compound can form a cross-linked bond during the curing step of the resin composition during the color filter manufacturing. By using it in combination with the oxime ester compound represented by the general formula (1) used in the present invention, the film strength of the cured film can be improved, the development resistance can be improved, the heat shrinkage of the cured film can be suppressed, and the adhesion to the substrate can be excellent.

The method of introducing an ethylenic double bond into the alkali-soluble resin can be appropriately selected from conventionally known methods. For example: on the carboxyl group of the alkali-soluble resin, a compound having an epoxy group and an ethylenic double bond (for example, glycidyl (meth)acrylate, etc.) is incorporated into the molecule, and an ethylenic double bond is introduced into the side chain. Bonding method; when introducing a structural unit having a hydroxyl group into a copolymer, a compound having an isocyanate group and an ethylenic double bond in the molecule is added, and an ethylenic double bond is introduced into the side chain.

The alkali-soluble resin of the present invention may further contain, for example, methyl (meth)acrylate, ethyl (meth)acrylate, etc., structural units having ester groups and other structural units. The structural unit having an ester group not only has the function of suppressing alkali-soluble components of the photosensitive colored resin composition for color filters, but also has the function of enhancing the solvent solubility (and solvent resolubility) of the components.

The alkali-soluble resin of the present invention is preferably an acrylic resin having a carboxyl-containing structural unit, an acrylic copolymer with a hydrocarbon ring-containing structural unit, and a styrene-acrylic copolymer, and more preferably contains a carboxyl-containing structural unit , Acrylic resins such as acrylic copolymers and styrene-acrylic copolymers with structural units with hydrocarbon rings and structural units with ethylenic double bonds.

Alkali-soluble resins can become alkali-soluble resins with required properties by appropriately adjusting the filling amount of each constituent unit.

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

If the ratio of the carboxyl group-containing ethylenically unsaturated monomer exceeds the above lower limit, the obtained coating film will have sufficient solubility in the alkali developer, and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is above the upper limit If the value is less than the value, when developing with an alkali developer, the formed pattern will be less likely to fall off the substrate, or the pattern surface film will tend to be rough.

Furthermore, it is preferable to use acrylic copolymers and styrene-acrylic copolymers, which are structural units of alkali-soluble resins having ethylenic double bonds, in combination with acrylic resins having epoxy groups and ethylenic double bonds. The compound is preferably 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass relative to the loading amount of the carboxyl group-containing ethylenically unsaturated monomer.

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

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

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited. For example, an epoxy resin obtained by reacting an epoxy compound with a monocarboxylic acid containing an unsaturated group and an acid anhydride is preferably used. (Meth)acrylate compound.

Epoxy compounds, unsaturated group-containing monocarboxylic acids and acid anhydride systems can be appropriately selected from known ones and used. The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, respectively, and may use 2 or more types together.

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

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

When the side chain of the alkali-soluble resin has an ethylenic unsaturated group, the equivalent of the ethylenic unsaturated bond can be obtained by combining the oxime ester compound represented by the above general formula (1) used in the present invention to increase the strength of the cured film, From the viewpoint of effects such as improvement of development resistance and excellent adhesion to the substrate, the range is preferably in the range of 100 to 2000, and more preferably in the range of 140 to 1500. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesiveness are excellent. Moreover, if it is 100 or more, the ratio of other structural units, such as the structural unit which has a carboxyl group, the structural unit which has a hydrocarbon ring, etc. relatively increases, and it is excellent in developability and heat resistance. The oxime ester compound represented by the general formula (1) used in the present invention preferably adopts the aforementioned content and combination.

The "ethylenically unsaturated bond equivalent" here refers to the weight average molecular weight of the average ethylenically unsaturated bond of 1 mol in the alkali-soluble resin, as shown in the following formula (1): Unsaturated bond equivalent (g/mol)=W(g)/M(mol)

(In the formula (1), W system represents the mass (g) of the alkali-soluble resin; M system 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 calculated by measuring the number of ethylenic double bonds contained in an average of 1 g of an alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992, for example.

The alkali-soluble resin used in the photosensitive colored resin composition for color filters can be used singly or in combination of two or more. The content is not particularly limited. Compared with the photosensitive color filter for color filters, the alkali-soluble resin The total solid content of the colored resin composition is preferably in the range of 5 mass% to 60 mass% of the alkali-soluble resin, and more preferably 10 mass% to 40 mass%. If the alkali-soluble resin content exceeds the above lower limit value, sufficient alkali developability can be obtained, and if the alkali-soluble resin content is below the above upper limit value, 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 prepared before the polymerization can be carried out by using the above-mentioned photoinitiator. The rest is not particularly limited, and it is usually best to use a compound having two or more ethylene The compound with a sexually unsaturated double bond is particularly preferably a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups.

Such a polyfunctional (meth)acrylate system can be appropriately selected and used from conventionally known materials. Specific examples include those described in JP 2013-029832 A, etc.

These polyfunctional (meth)acrylates can be used individually by 1 type or in combination of 2 or more types. In addition, when the photosensitive colored resin composition for color filters of the present invention requires excellent photocurability (high sensitivity), the polyfunctional (meth)acrylate preferably has 3 (trifunctional) or more polymerizable double bonds Among them, poly(meth)acrylates of polyhydric alcohols with a valence of trivalent or higher, and these dicarboxylic acid modifiers are preferred. Specific examples include trimethylolpropane tri(meth)acrylate, pentaerythritol tri (Meth) acrylate, succinic acid modification of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Succinic acid modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

The content of the photopolymerizable compound used in the photosensitive colored resin composition for color filters is not particularly limited, and the amount of the photopolymerizable compound is relative to the total solid content of the photosensitive colored resin composition for color filters. The compound is preferably in the range of 5% by mass to 60% by mass, more preferably in the range of 10% by mass to 40% by mass. If the content of the photopolymerizable compound is more than the above lower limit, photocuring is sufficiently advanced and the exposed portion can be prevented from eluting during development, and if the content of the photopolymerizable compound is less than the above upper limit, the alkali developability is sufficient.

In the photosensitive colored resin composition for color filters, the ratio of the content of the photopolymerizable compound used and the content of the photoinitiator to the content of the photoinitiator is improved in terms of excellent curability and residual film rate, and improved electrical reliability From the viewpoint of, relative to 100 parts by mass of the photopolymerizable compound, the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, More preferably, it is 30 parts by mass or less.

[Solvent]

The solvent used in the present invention does not react with each component in the photosensitive colored resin composition for a color filter, but it can dissolve or disperse the organic solvent, and the rest is not particularly limited. The solvent system can be used individually or in combination of 2 or more types.

Specific examples of solvents include, for example, alcohol-based solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxyethanol Carbitol-based solvents; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, hydroxypropionate Ester solvents such as ethyl propionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate, etc.; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, cyclohexanone and 2-heptanone; ethyl methoxyacetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, acetic acid Glycol ether acetate solvents such as -3-methoxybutyl ester and ethoxy ethyl acetate; methoxy ethoxy ethyl acetate, ethoxy ethoxy ethyl acetate, butyl carbitol acetic acid Carbitol acetate solvents such as esters (BCA); diacetate esters such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether and other glycol ether solvents; N,N-dimethyl Aprotic amide solvents such as formamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; cyclic ether-based solvents such as tetrahydrofuran; benzene , Toluene, xylene, naphthalene and other unsaturated hydrocarbon solvents; N-heptane, N-hexane, N-octane and other saturated hydrocarbon solvents; Toluene, xylene and other aromatic hydrocarbons and other organic solvents. Among these solvents, from the viewpoint of solubility of other components, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used. Among them, the solvent used in the present invention is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), from the viewpoints of solubility of other components and coating suitability. Choose one or more from the group consisting of 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate.

In the photosensitive colored resin composition for color filters of the present invention, the solvent content can be appropriately set within the range where the colored layer is formed with high accuracy. It is generally preferably in the range of 55% to 95% by mass, and more preferably in the range of 65% to 88% by mass relative to the total amount of the photosensitive colored resin composition for color filters containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

[Dispersant]

In the photosensitive colored resin composition for a color filter of the present invention, the above-mentioned color material is preferably used after being dispersed in a solvent with a dispersant. In the present invention, the dispersant system can be appropriately selected and used from conventionally known dispersants. As the dispersant system, for example, cationic, anionic, nonionic, amphoteric, silicone, fluorine, and other surfactants can be used. Among the surfactants, a polymer dispersant is preferred from the viewpoint of obtaining uniform and fine dispersion.

Examples of polymer dispersants include: (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts and (partial) ammonium of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid. Salts, (part of) alkylamine salts; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates, and modifications thereof; polyurethanes; unsaturated polyamides; polysilicones Oxyanes; long-chain polyamino amide phosphates; polyethylene imine derivatives [Using the reaction of poly(lower alkylene imine) with a polyester containing free carboxyl groups to obtain amides, these bases ]; Polyallylamine derivatives (make polyallylamine, and from the polyester with free carboxyl group, polyamide or ester and amide co-condensate (polyester amide) and other three kinds of compounds selected at least one Compound, reaction product obtained by reaction), etc.

The polymer dispersant is preferably a polymer dispersant with an amine value that contains nitrogen atoms in the main chain or side chain from the viewpoint of being able to disperse the above-mentioned color materials properly and having good dispersion stability. From the viewpoints of no precipitation of foreign matter during coating film formation and improvement in brightness and contrast, it is more preferable to use a polymer dispersant composed of a polymer having tertiary amine-containing repeating units.

The repeating unit with tertiary amine is the part that has affinity with the above-mentioned color material. A polymer dispersant composed of a polymer having a tertiary amine-containing repeating unit usually contains a repeating unit that will become a site having affinity with the solvent. Polymers with tertiary amine-containing repeating units are excellent in heat resistance and capable of forming high-brightness coatings. It is particularly preferable to have: block parts composed of tertiary amine repeating units and solvent affinity The block copolymer of the sexual block part.

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

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

(In general formula (I), R ¹ is a hydrogen atom or a methyl group; Q is a divalent linking group; R ² is an alkylene group with 1 to 8 carbon atoms, -[CH(R ⁵ )-CH(R ⁶ ) -O] _x -CH(R ⁵ )-CH(R ⁶ )-or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -as shown in the divalent organic group; R ³ and R ⁴ are Each independently represents a chain or cyclic hydrocarbon group that may be substituted, or R ³ and R ⁴ are bonded to each other to form a cyclic structure. R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.

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

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

^{The divalent organic group R 2} of the above general formula (I) is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH(R ⁶ )-O] _x -CH(R ⁵ )-CH( R ⁶ )-or-[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -. The above-mentioned alkylene series with 1 to 8 carbon atoms can be arbitrarily linear or branched, such as: methylene, vinyl, trimethylene, propylene, various butylenes, various pentylenes, various extensions Hexyl, various octyl groups, etc.

R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.

The above R ^2, from the viewpoint of dispersibility, the preferred stretch-based carbon number of an alkyl group having 1 to 8, wherein, R ² more preferably a methylene group based, extending ethyl, propyl stretched, stretch-butyl, particularly preferably Department of methylene and ethylene.

In the above general formula (I), ^{the cyclic structure formed by R 3} and R ⁴ being bonded to each other can include, for example, a five- to seven-membered ring nitrogen-containing heterocyclic monocyclic ring, or a condensation formed by the condensation of these two ring. The nitrogen-containing heterocyclic ring is preferably not aromatic, and it is more preferably a saturated ring.

The repeating unit system represented by the above general formula (I) may, for example, be dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate , (Meth)acrylic acid diethylaminopropyl ester and other (meth)acrylates containing alkyl substituted amino groups, etc.; dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth) (Meth)acrylamide containing alkyl substituted amino groups such as acrylamide. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferable to use dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl ( (Meth)acrylamide.

In the block portion composed of the above-mentioned tertiary amine repeating unit, 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, it is preferable to contain 3 to 100, more preferably 3 to 50, and particularly preferable to contain 3 to 30.

In a block copolymer having a block portion (hereinafter referred to as "A block") constituted by the above-mentioned tertiary amine repeating unit (hereinafter referred to as "A block"), and a block portion having solvent affinity (hereinafter referred to as "B block"), it has The solvent-affinity block part does not have the structural unit represented by the above general formula (I) from the viewpoint of making the solvent affinity good and improving the dispersibility, but has the ability to copolymerize with the above general formula (I) The solvent affinity block part of the constituent unit. In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and examples thereof include AB block copolymers, ABA block copolymers, and BAB block copolymers. Among them, from the viewpoint of excellent dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

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

The number of structural units constituting the solvent affinity block portion may be appropriately adjusted within a range that can improve the dispersibility of the color material. Among them, from the viewpoint that the solvent affinity site and the color material affinity site can effectively function and improve the dispersibility of the color material, the number of structural units constituting the solvent affinity block portion is preferably 10 to 200, and more preferably 10 ~100, especially good series 10~70.

The solvent-affinity block part system may be selected as long as it exhibits the function of the solvent-affinity part, and the repeating unit system constituting the solvent-affinity block part may be composed of a single type or may contain two or more types of repeating units.

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

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

When the amine value is within the above range, the viscosity with time stability and heat resistance are excellent, and the alkali developability and solvent resolubility are also excellent. If the amine value of the dispersant is higher, the dispersibility and dispersion stability will be improved, and the solvent solubility and solvent re-solubility will be improved, the compatibility with other components will be better, the linearity of the fine line pattern of the colored layer will be improved, and the Easily suppress the trembling of tiny holes. In the present invention, the amine value of the dispersant is particularly preferably 80 mgKOH/g or more, and more preferably 90 mgKOH/g or more. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersant is preferably 110 mgKOH/g or less, and more preferably 105 mgKOH/g or less.

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

The lower limit of the acid value of the dispersant used in the present invention is preferably 1 mgKOH/g or more from the viewpoint of the development residue suppression effect. Among them, the acid value of the dispersant is more preferably 2 mgKOH/g or more from the viewpoint that the effect of suppressing the development residue is more excellent. In addition, the acid value of the dispersant used in the present invention can prevent deterioration of development adhesion and deterioration of solvent resolubility, improve the linearity of the fine line pattern of the colored layer, and easily suppress the chattering of micropores. The upper limit of the value is preferably 18 mgKOH/g or less. Among them, the acid value of the dispersant is more preferably 16 mgKOH/g or less, and particularly preferably 14 mgKOH/g or less, from the viewpoint of good development adhesion and solvent resolubility.

The dispersant used in the present invention preferably has an acid value of the block copolymer before salt formation is 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. The reason is that the effect of suppressing development residue can be improved. In addition, the upper limit of the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 16 mgKOH/g or less, and particularly preferably 14 mgKOH/g or less. The reason is that the developing adhesion and solvent re-solubility are good.

Furthermore, in the present invention, the glass transition temperature of the dispersant is preferably 30°C or higher from the viewpoint of improving development adhesion. That is, regardless of the block copolymer before the formation of the dispersant-based salt or the salt-type block copolymer, the glass transition temperature is preferably 30°C or higher. If the glass transition temperature of the dispersant is low, especially close to the temperature of the developer (usually around 23°C), there is a possibility that the development adhesiveness may decrease. The reason is that if the glass transition temperature is close to the temperature of the developer, the movement of the dispersant during development becomes larger, and as a result, it is estimated that the development adhesion will deteriorate. When the glass transition temperature reaches 30°C or higher, the movement of the dispersant molecules during development is suppressed, so it is presumed that the deterioration of the development adhesion will be suppressed.

The glass transition temperature of the dispersant is particularly preferably 32°C or higher, and more preferably 35°C or higher, from the viewpoint of development adhesion. On the other hand, from the viewpoint of operability during use such as ease of precision weighing, it is preferably 200°C or lower.

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

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

Here, the block part is set to be copolymerized from n monomer components of i=1 to n. Xi is the weight fraction of monomer i (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the monomer of monomer i. However, the Σ system is set as the sum of i=1 to n. In addition, the monomer glass transition temperature value (Tgi) of each monomer can be the value of the Polymer Handbook (3 ^rd Edition) (by J. Brandrup, EHImmergut (Wiley-Interscience, 1989)).

If the concentration of the color material is increased and the content of the dispersant is increased, the amount of bonding agent is relatively reduced, and therefore the colored resin layer is easier to peel off from the base substrate during development. When the dispersant contains the B block of the unit derived from the carboxyl group-containing monomer, and has the above-mentioned specific acid value and glass transition temperature, the development adhesion can be improved. If the acid value is too high, the developability is excellent, but the polarity is conversely too high, and it is estimated that peeling is likely to occur during development.

From the above, the dispersant of the present invention has excellent dispersion stability of color materials and improved contrast. When forming a coloring resin composition containing the oxime ester compound represented by the above general formula (1), the dispersant of the present invention can inhibit the generation of development residues and the resolving of solvents. From the viewpoints of excellent solubility and higher developing adhesion, and from the viewpoints of easy formation of fine pores with excellent shape, easy suppression of tremor of fine pores, and development residues, it is preferable to contain the structure represented by the above general formula (I), A polymer with an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less, an acid value of 1 mgKOH/g or more and 18 mgKOH/g or less, and a glass transition temperature of 30°C or more.

The above-mentioned carboxyl group-containing single system can use a monomer that can be copolymerized with a monomer having a structural unit represented by the general formula (I) and contains an unsaturated double bond and a carboxyl group. Examples of such a single system include: (meth)acrylic acid, vinyl benzoate, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamon Acid, acrylic acid dimer, etc. In addition, it is also possible to use, for example: (meth)acrylic acid-2-hydroxyethyl and other monomers with hydroxyl groups, and the addition of cyclic dehydrates such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride. Into a reactant; or ω-carboxy-polycaprolactone mono(meth)acrylate, etc. In addition, monomers containing acid anhydride groups such as maleic anhydride, itaconic anhydride, and citraconic anhydride, which are precursors of carboxyl groups, may also be used. Among them, from the viewpoints of copolymerization, cost, solubility, glass transition temperature, etc., (meth)acrylic acid is more preferable.

In the block copolymer before salt formation, the ratio of the constituent units derived from the carboxyl group-containing monomer can be appropriately set as long as the acid value of the block copolymer falls within the above-mentioned specific acid value range. It is limited, with respect to the total mass of the total constituent units of the block copolymer, it is preferably 0.05% by mass to 4.5% by mass, and more preferably 0.07% by mass to 3.7% by mass.

When the content ratio of the structural unit derived from the carboxyl group-containing monomer is above the above lower limit, the development residue suppression effect can be exhibited, and when the content is below the above upper limit, it is possible to prevent deterioration of development adhesion and solvent re-dissolution Sexual deterioration.

In addition, the structural unit derived from the carboxyl group-containing monomer may have the above-mentioned specific acid value, and may be composed of a single type, or may contain two or more types of structural units.

In addition, 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 the development adhesion, the monomer monomer has a glass transition temperature (Tgi) of 10°C or higher. , The total content in the B block is preferably 75% by mass or more, more preferably 85% by mass or more.

In the above-mentioned block copolymer, the ratio m/n of the unit number m of the A block constituent unit and the unit number n of the B block constituent unit is relatively higher from the viewpoint of color material dispersibility and dispersion stability. The best system is in the range of 0.05 to 1.5, and the better system is in the range of 0.1 to 1.0.

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

Here, the weight average molecular weight (Mw) is obtained by using a gel permeation chromatography analyzer (GPC) based on a standard polystyrene conversion value. In addition, the macromonomers, salt-type block copolymers, and graft copolymers used as raw materials for block copolymers are also implemented under the above-mentioned conditions.

A specific example of a block copolymer having a block portion composed of such a tertiary amine repeating unit and a block portion having solvent affinity is preferably a block copolymer described in Japanese Patent No. 4911253 .

The polymer containing the tertiary amine repeating unit is used as a dispersant. When dispersing the color material, the content of the polymer containing the tertiary amine repeating unit is preferably 15 mass parts relative to 100 parts by mass of the color material. Parts ~ 300 parts by mass, more preferably 20 parts by mass to 250 parts by mass. If it is in the above range, both dispersibility and dispersion stability are excellent, and the effect of improving contrast is high.

In the present invention, from the viewpoint of color material dispersibility and dispersion stability, it is also preferable to form a salt from the polymer containing the above-mentioned tertiary amine repeating unit at least part of the amine groups with an organic acid compound or halogenated hydrocarbon, Used as a dispersant (hereinafter, this type of polymer is referred to as "salt type polymer").

Among them, from the viewpoint of excellent color material dispersibility and dispersion stability, it is preferable to contain a polymer system block copolymer having tertiary amine repeating units, and the above-mentioned organic acid compounds are phenylphosphonic acid and phenylphosphine. Acidic organic phosphorus compounds such as phosphonic acid. Specific examples of the organic acid compound used in such a dispersant include, for example, the organic acid compound described in JP 2012-236882 A and the like.

Furthermore, the halogenated hydrocarbon is preferably at least one of halogenated allyl groups such as allyl bromide and chlorotoluene and halogenated aralkyl groups from the viewpoint of excellent color material dispersibility and dispersion stability. 1 kind.

When using a dispersant, the content is on the premise that the color material can be dispersed uniformly, and the rest is not particularly limited. For example, 1% by mass can be used relative to the total solid content of the photosensitive colored resin composition for color filters ~40% by mass. In addition, with respect to the total solid content of the photosensitive colored resin composition for color filters, it is preferably blended at a ratio of 2% by mass to 30% by mass, and more preferably blended at a ratio of 3% by mass to 25% by mass. . If it exceeds the above lower limit, 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 better. Moreover, if it is below the said upper limit, developability will become favorable. Especially when forming a coloring layer with a high color material concentration, the dispersant content relative to the total solid content of the photosensitive coloring resin composition for color filters is preferably 2% to 25% by mass, and more The best system is blended at a ratio of 3% by mass to 20% by mass.

[Antioxidants]

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 is combined with the oxime ester compound represented by the above general formula (1) and contains antioxidants, thereby improving heat resistance and suppressing exposure and post-baking. The brightness of the film is reduced, so it can increase the brightness. In addition, when the cured film is formed with tiny holes, it will not damage the hardenability. It can control the excessive chain reaction of free radicals in the tiny holes, so it can more easily form the required shape of the tiny holes.

The antioxidant used in the present invention is not particularly limited, and can be appropriately selected from conventionally known ones. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc., from the viewpoint of heat resistance and good micropore shapes In general, it is preferable to use hindered phenol-based antioxidants.

The "hindered phenol-based antioxidant" refers to an antioxidant having at least one phenol structure, and having at least one of the 2-position and 6-position of the hydroxyl group of the phenol structure substituted with a substituent having 4 or more carbon atoms.

(商品名：IRGANOX 565、BASF製)、2,2'-硫代二乙基雙[3-(3,5-二第三丁基-4-羥苯基)丙酸酯](商品名：IRGANOX 1035、BASF製)、1,2-雙[3-(4-羥-3,5-二第三丁基苯基)丙醯基]肼(商品名：IRGANOX MD1024、BASF製)、3-(4-羥-3,5-二異丙基苯基)丙酸辛酯(商品名：IRGANOX 1135、BASF製)、4,6-雙(辛硫基甲基)-鄰甲酚(商品名：IRGANOX 1520L、BASF製)、N,N'-六亞甲基雙[3-(3,5-二第三丁基-4-羥苯基)丙醯胺](商品名：IRGANOX 1098、BASF製)、1,6-己二醇雙[3-(3,5-二第三丁基-4-羥苯基)丙酸酯](商品名：IRGANOX 259、BASF製)、1-二甲基-2-[(3-第三丁基-4-羥-5-甲基苯基)丙醯氧基]乙基]2,4,8,10-四

螺[5.5]十一烷(商品名：ADK STABA0-80、ADEKA製)、雙(3-第三丁基-4-羥-5-甲基苯丙酸)乙烯雙(氧乙烯)(商品名：IRGANOX 245、BASF製)、1,3,5-三[[4-(1,1-二甲基乙基)-3-羥-2,6-二甲基苯基]甲基]-1,3,5-三

-2,4,6(1H,3H,5H)-三酮(商品名：IRGANOX 1790、BASF製)、2,2'-亞甲基雙(6-第三丁基-4-甲基酚)(商品名：SUMIRAIZA MDP-S、住友化學製)、6,6'-硫代雙(2-第 三丁基-4-甲基酚)(商品名：IRGANOX 1081、BASF製)、3,5-二第三丁基-4-羥苄基膦酸二乙酯(商品名：IRGAMOD 195、BASF製)、丙烯酸-2-第三丁基-4-甲基-6-(2-羥-3-第三丁基-5-甲基苄基)苯酯(商品名：SUMIRAIZA GM、住友化學製)、4,4'-硫代雙(6-第三丁基-間甲酚)(商品名：SUMIRAIZA WX-R、住友化學製)、6,6'-二第三丁基-4,4'-亞丁基二間甲酚(商品名：ADEKA STAB AO-40、ADEKA製)等。其他尚可使用具受阻酚構造的寡聚式及聚合物式化合物等。 Specific examples of hindered phenol-based antioxidants include, for example, dibutylhydroxytoluene (BHT), neopentylerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid Esters] (trade name: IRGANOX 1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114, BASF product), 2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: IRGANOX 1330, BASF product), 6-(4-hydroxy-3 ,5-Di-tert-butylanilino)-2,4-bis(octylthio)-1,3,5-tri

(Trade name: IRGANOX 565, manufactured by BASF), 2,2'-thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1035, manufactured by BASF), 1,2-bis[3-(4-hydroxy-3,5-di-tert-butylphenyl)propanyl]hydrazine (trade name: IRGANOX MD1024, manufactured by BASF), 3- (4-hydroxy-3,5-diisopropylphenyl) octyl propionate (trade name: IRGANOX 1135, manufactured by BASF), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX 1520L, manufactured by BASF), N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] (trade name: IRGANOX 1098, manufactured by BASF ), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259, manufactured by BASF), 1-dimethyl -2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetra

Spiro[5.5]undecane (trade name: ADK STABA0-80, manufactured by ADEKA), bis(3-tertiarybutyl-4-hydroxy-5-methylphenylpropionic acid) ethylene bis(oxyethylene) (trade name : IRGANOX 245, manufactured by BASF), 1,3,5-tris[[4-(1,1-dimethylethyl)-3-hydroxy-2,6-dimethylphenyl]methyl]-1 ,3,5-three

-2,4,6(1H,3H,5H)-trione (trade name: IRGANOX 1790, manufactured by BASF), 2,2'-methylenebis(6-tertiarybutyl-4-methylphenol) (Trade name: SUMIRAIZA MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF), 3,5 -Diethyl di-tert-butyl-4-hydroxybenzylphosphonate (trade name: IRGAMOD 195, manufactured by BASF), acrylic acid-2-tert-butyl-4-methyl-6-(2-hydroxy-3 -Tertiary butyl-5-methylbenzyl) phenyl ester (trade name: SUMIRAIZA GM, manufactured by Sumitomo Chemical), 4,4'-thiobis(6-tertiarybutyl-m-cresol) (trade name : SUMIRAIZA WX-R, manufactured by Sumitomo Chemical), 6,6'-di-tertiarybutyl-4,4'-butylene xylenol (trade name: ADEKA STAB AO-40, manufactured by ADEKA), etc. Other oligomeric and polymer compounds that can be used with hindered phenol structures.

Furthermore, in the present invention, latent antioxidants can also be used as antioxidants. The so-called "potential antioxidant" in the present invention is a compound having a protective group that can be removed by heating, and a compound that exhibits an antioxidant function by the removal of the protective group. Among them, it is best to heat the protective group at a temperature of 150°C or higher so that the protective group will be easily removed. Since the latent antioxidant does not have the antioxidant function during exposure, the free radicals generated by the photoinitiator are not deactivated, which can easily suppress the decrease in sensitivity, suppress the thinning of the line width and increase the residual film rate. On the other hand, in the heating step performed after exposure, since the protective group is released and exhibits an anti-oxidation effect, it is possible to suppress the fading of color materials and the like, and to obtain a high-brightness colored layer.

The latent antioxidant preferably used in the present invention, from the standpoint of heat resistance and good micropore shape, can be, for example, the phenolic hydroxyl group of the hindered phenol antioxidant, which can be replaced by a protective group that can be released by heating. The potential hindered phenol-based antioxidants to be protected, specific examples include the following chemical formulas (a) to (c), etc., but are not limited to these.

[Chemical formula 11] Chemical formula (a)

The method for producing the above-mentioned potential antioxidant is not particularly limited. For example, Japanese Patent Laid-Open No. 57-111375, Japanese Patent Laid-Open Hei 3-173343, Japanese Patent Laid-Open Hei 6-128195, Japanese Patent Laid-Open Hei 7-206771, JP Hei 7-252191, The phenolic compounds produced by the methods described in the JP 2004-501128 publications can be obtained by reacting with acids such as acid anhydrides, acid chlorides, Boc reagents, haloalkane compounds, chlorosilane compounds, and allyl ether compounds. In addition, commercially available products can also be used.

The protective groups that can be removed by heating include, for example, acid anhydrides, acid chlorides, Boc reagents, haloalkane compounds, chlorosilane compounds, or allyl ether compound reaction residues. Typical systems can be, for example, tertiary butoxy Carbonyl.

The content when the antioxidant is used is not particularly limited. For example, it can be 0.1% by mass to 20% by mass relative to the total solid content of the photosensitive colored resin composition for color filters. In addition, from the viewpoint of fully exerting the effect of using the photoinitiator together, it is preferable to blend 0.2% by mass to 10% by mass relative to the total solid content of the photosensitive colored resin composition for color filters. More preferably, the ratio is 0.3% to 5% by mass.

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

On the other hand, from the viewpoint of maintaining appropriate sensitivity, it is preferably 300 parts by mass or less, and more preferably 200 parts by mass or less with respect to the total of 100 parts by mass of the photoinitiator used in the present invention.

[Optionally add ingredients]

The photosensitive colored resin composition for color filters may contain various additives as needed. Examples of additives include polymerization terminator, chain transfer agent, leveling agent, plasticizer, surfactant, defoamer, silane coupling agent, ultraviolet absorber, adhesion promoter, and the like.

Specific examples of surfactants and plasticizers include those described in Japanese Patent Laid-Open 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 content other than the color material (hereinafter also referred to as "P/V ratio"), when forming the coloring layer of the color filter, only It can be the desired color, and the rest is not particularly limited. It is preferably within the range of 0.05 or more and 1.00 or less, more preferably within the range of 0.10 or more and 0.80 or less, particularly preferably within the range of 0.15 or more and 0.75 or less, and the most Preferably, it is in the range of 0.20 or more and 0.70 or less. When the P/V ratio is in the above range, a photosensitive colored resin composition for color filters that can form a coloring layer that emits the desired color can be obtained, and the above-mentioned photosensitive colored resin composition for color filters The substance can be uniformly dispersed.

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

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

In the case of a blue colored resin composition, from the viewpoint of desired color development, the P/V ratio is preferably 0.24 or more, more preferably 0.34 or more, and particularly preferably 0.41 or more. Moreover, it is preferably 1.0 or less. If the respective values exceed the above lower limit values, the color density of the photosensitive colored resin composition for color filters can be increased, and the color filter pixels can have higher color rendering and lower film thickness. Moreover, if each is below the upper limit value, the storage stability is excellent, and a colored layer having sufficient hardness and adhesion to the substrate can be obtained.

<Manufacturing Method of Photosensitive Colored Resin Composition for Color Filter>

The method for producing a photosensitive colored resin composition for a color filter of the present invention contains: a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent (preferably a dispersant), an antioxidant, and Depending on the various additional components to be used, from the viewpoint of enhancing contrast, it is preferable to use a method of uniformly dispersing the color material in a solvent using a dispersant, and it can be prepared by mixing using a known mixing means.

The preparation method of the resin composition may include, for example: (1) First, a color material and a dispersant are added to a solvent to prepare a color material dispersion, and then an alkali-soluble resin, a photopolymerizable compound, The photoinitiator and the method of adding various ingredients as required; (2) In the solvent, simultaneously throw in the color material, dispersant, alkali-soluble resin, photopolymerizable compound, photoinitiator and use as required (3) In the solvent, add: dispersant, alkali-soluble resin, photopolymerizable compound, photoinitiator, and various additives as needed. After mixing, add Method of dispersing color materials; (4) Add color materials, dispersants and alkali-soluble resins in a solvent to prepare a color material dispersion, and then further add alkali-soluble resins, solvents, and photopolymerization to the dispersion. Sexual compounds, photoinitiators, and various additional ingredients as needed, and mixing methods, etc.

Among these methods, the above-mentioned methods (1) and (4) are preferred from the viewpoint of effectively preventing the color material from agglomerating and being able to be uniformly dispersed.

The method of preparing the color material dispersion liquid can be appropriately selected and used from conventionally known dispersion methods. For example: (1) The dispersant is mixed in the solvent and stirred in advance to prepare a dispersant solution, and then the organic acid compound is mixed as necessary to make the amine group of the dispersant and the organic acid compound form a salt, and then it is combined with the color material And other ingredients as needed, using a known mixer or dispersing machine to perform the dispersion method; (2) The dispersant is mixed in the solvent and stirred to prepare a dispersant solution, and then the color materials, organic acid compounds as required and as required (3) Mix the dispersant in a solvent and stir to prepare a dispersant solution, and then mix the color materials and other components as necessary, using a known mixer or After the dispersion machine forms a dispersion, a method of adding an organic acid compound if necessary, etc.

The dispersing machine system used to perform the dispersion treatment can include, for example: roller crushers such as two-roll mills and three-roll mills; ball mills, vibrating ball mills, etc.; paint regulators, continuous disc type bead mills, continuous ring-shaped beads Bead mills such as mills. The better dispersion conditions of the bead mill are that the diameter of the balls used is preferably 0.03mm~2.00mm, more preferably 0.10mm~1.0mm.

II. Color filter

The color filter of the present invention is a color filter having at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is made of the above-mentioned photosensitive colored resin for a color filter of the present invention The colored layer formed by the hardened substance of the composition.

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

(Colored layer)

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

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

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

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

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

First, the aforementioned photosensitive colored resin composition for color filters of the present invention is applied using coating means such as spray coating, dip coating, bar coating, roll coating, spin coating, and die coating. It is spread on the substrate described later to form a wet coating film. Among them, it is preferable to use a spin coating method or a die coating method.

Next, use a hot plate, oven, etc., to dry the wet coating film, and then expose it through a mask with a predetermined pattern, and photopolymerize the alkali-soluble resin and photopolymerizable compound to form a cured coating film. . Examples of the light source used in the exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and other ultraviolet light, electron beams, and the like. The amount of exposure is adjusted appropriately according to the light source used and the thickness of the coating film.

Furthermore, after exposure, to promote the polymerization reaction, heat treatment may also be performed. The heating conditions are appropriately selected according to the blending ratio of the respective components in the photosensitive colored resin composition for color filters used, the thickness of the coating film, and the like.

Secondly, a developing solution is used to perform a development process, and by dissolving and removing the unexposed part, a coating film is formed according to the desired pattern. The developer is usually a solution in which an alkali is dissolved in water or a water-soluble solvent. Surfactant etc. can also be added in an appropriate amount to this alkaline solution.

Furthermore, a general method can be adopted for the development method.

After the development treatment, washing with a developer solution and drying of the cured coating film of the photosensitive colored resin composition for color filters are usually performed to form a colored layer. In addition, after the development treatment, in order to fully harden the coating film, heat treatment may be applied. The heating conditions are not particularly limited, and can be appropriately selected according to the application of the coating film.

Furthermore, when the color filter of the present invention is formed in a color filter on array (COA, Color Filter on Array) structure, etc., when the above-mentioned development process is performed, minute holes may be formed in the above-mentioned colored layer. . Since the present invention uses the above-mentioned photosensitive colored resin composition for color filters, it is possible to easily form required minute holes in the colored layer. The shape of the above-mentioned micropores can be appropriately selected according to the application, and is not particularly limited. The present invention can form micropores with a size of about 10 μm×10 μm to 30 μm×30 μm, for example. In addition, the shape of the micropores is not particularly limited, and may be, for example, circular, elliptical, polygonal, or the like.

The method of forming minute holes in the colored layer can be, for example, the mask used when forming the colored layer. A patterned light for forming a minute mask for forming minute holes is arranged in the opening pattern of a patterned mask capable of forming a fine line pattern. The method of hood.

(Shading part)

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

The pattern shape of the light-shielding portion is not particularly limited, and may be, for example, a stripe shape, a matrix shape, or the like. For the light-shielding part, a metal thin film such as chromium can be formed by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, for example, a method of developing and patterning using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, and a method of applying heat to the photosensitive resist Transfer method, etc.

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

(Substrate)

As the substrate, for example, a transparent substrate, a silicon substrate, and a thin film of aluminum, silver, silver/copper/palladium alloy, etc. formed on the transparent substrate or the silicon substrate described later are used. On these substrates, other color filter layers, resin layers, transistors such as TFTs, and circuits, etc. can also be formed.

The transparent substrate of the color filter of the present invention is based on a substrate that is transparent to visible light, and the rest is not particularly limited, and the transparent substrate used in general color filters can be used. Specific examples include: transparent rigid materials without flexibility, such as quartz glass, alkali-free glass, and synthetic quartz plates; or transparent resin films, optical resin plates, flexible glass, and other transparent and flexible materials with flexibility. Sex material.

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

In addition, the color filter of the present invention can also be formed with, for example, protective layers, transparent electrode layers, alignment films, alignment protrusions, columnar spacers, etc., in addition to the above-mentioned substrate, light-shielding portion, and coloring layer.

III. Display device

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

[Liquid crystal display device]

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

The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 shows a schematic diagram of an example of the liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention is provided with a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a counter substrate 20 formed between the color filter 10 and the counter substrate 20. Liquid crystal layer 30.

In addition, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2, and a known structure of a liquid crystal display device that generally uses color filters may be adopted.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and the driving method used in general liquid crystal display devices can be adopted. Such driving methods can be, for example: TN method, IPS method, OCB method, MVA method and so on. In the present invention, any of these methods are suitable for use.

Furthermore, the counter substrate can be appropriately selected according to the driving method of the liquid crystal display device of the present invention.

Furthermore, the liquid crystal system constituting the liquid crystal layer can be adapted to the driving method of the liquid crystal display device of the present invention, etc., and various liquid crystals with different dielectric anisotropies and mixtures thereof can be used.

The method for forming the liquid crystal layer can be a method used in general liquid crystal cell production methods, such as a vacuum injection method, a liquid crystal dropping method, and the like. After the liquid crystal layer is formed by the above method, by gradually cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.

[Organic Light Emitting Display Device]

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

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

The layering method of the organic light-emitting body 80 may include, for example, 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 color filter; A method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60 and the like. 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 of the organic light-emitting body 80, and other structures, can use known materials as appropriate. The organic light emitting display device 100 manufactured in this way can be applied to, for example, passively driven organic EL displays and actively driven organic EL displays.

In addition, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and a well-known configuration of organic light-emitting display devices that generally use color filters may also be adopted.

[Example]

Hereinafter, a specific description will be given of exemplary embodiments of the present invention. However, the present invention is not limited by these descriptions.

The structure of the obtained compound was measured by 1H- and 13C-NMR mass spectrometry using a nuclear magnetic resonance device (Bruker BioSpin, AVANCEIII HD500MHz), and a liquid chromatograph/mass spectrometer (Shimadzu Corporation, LC-30A, Bruker Daltonics, micrOTOFQ2) quality analysis can be confirmed.

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

Dissolve 0.60 mol, 2.4 mol of potassium hydroxide, and 0.06 mol of potassium iodide in 500 ml of anhydrous dimethyl sulfoxide under nitrogen, maintain at 15°C, slowly add 1.33 mol of butane bromide over 2 hours, and reactants at 15°C Stir for 1 hour. Then, after adding 2 L of distilled water to the reactant and stirring for about 30 minutes, the product was extracted with 2 L of dichloromethane, and the extracted organic layer was washed twice with 2 L of distilled water. Next, the recovered organic layer was dried with anhydrous MgSO ₄ , and then the solvent was subjected to vacuum distillation to obtain the product, which was subjected to a silica gel column chromatography (developing solvent: ethyl acetate: n-hexane=1:20) After purification, the following intermediate A1 was obtained.

(2) Synthesis of Intermediate A2

Above intermediate A1 (0.11mol) was dissolved in 500ml of dichloromethane, cooled to -5 deg.] C, bradycardia was added AlCl _3: 0.13mol, depending on the reaction temperature was not raised manner, dropped over 1 hour by two bradycardia A solution composed of 15 ml of methyl chloride and 0.13 mol of cyclohexyl propyl chloride was stirred at -5°C for 1 hour. Then, the reactant was slowly poured into 500 ml of ice water, and after stirring for 30 minutes, the organic layer was washed with 200 ml of distilled water. Next, the recovered organic layer was subjected to vacuum distillation to obtain a product, which was subjected to purification with a silica gel column chromatography (developing solvent: ethyl acetate: n-hexane = 1:4) to obtain the following intermediate A2.

(3) Synthesis of Intermediate A3

烷中的(4N)HCl：25ml與亞硝酸異丁酯0.063mol，反應物經25℃攪拌6小時。然後，在反應溶液中添加醋酸乙酯200ml並攪拌30分鐘，而分離出有機層後，利用蒸餾水200ml洗淨。接著，所回收的有機層利用無水MgSO₄乾燥，再將溶劑施行減壓蒸餾而獲得生成物，利用矽膠管柱色層分析儀(展開溶劑：醋酸乙酯：正己烷=1：4)進行精製，獲得下述中間體A3。 The above intermediate A2 (0.042mol) was dissolved in 200ml of tetrahydrofuran (THF), and dissolved in 1,4-bis

(4N) HCl in alkane: 25ml and 0.063mol isobutyl nitrite, and the reactant was stirred at 25°C for 6 hours. Then, 200 ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes. After the organic layer was separated, it was washed with 200 ml of distilled water. Next, the recovered organic layer was dried with anhydrous MgSO ₄ , and then the solvent was subjected to vacuum distillation to obtain the product, which was purified by a silica gel column chromatography analyzer (developing solvent: ethyl acetate: n-hexane = 1:4) , The following intermediate A3 was obtained.

[化14]

(4) Synthesis of compound A

The above-mentioned intermediate A3 (0.056 mol) was dissolved in 200 ml of N-methyl-2-pyrrolidone (NMP) under a nitrogen environment, maintained at -5°C, 0.068 mol of triethylamine was added, and the reaction solution was stirred for 30 minutes. Then, a solution consisting of 0.068 mol of chloroacetate and 10 ml of N-methyl-2-pyrrolidone was slowly added over 30 minutes, and the reaction mixture was stirred for 30 minutes so that the temperature of the reactant would not rise. Then, 200 ml of distilled water was slowly added to the reactant and stirred for 30 minutes, and the organic layer was separated. Next, the recovered organic layer was dried with anhydrous MgSO ₄ , and the solvent was subjected to reduced pressure distillation to obtain a product, which was recrystallized using 1 L of ethanol and dried to obtain the following compound A.

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

Except that in the synthesis example 1 (1), instead of bromobutane, the same mole of bromoethane was used instead, and the purification using the silica gel column chromatography analyzer was not carried out, the rest were all in accordance with the synthesis example 1. In the same manner as in (1), the following intermediate B1 was obtained.

(2) Synthesis of intermediate B2

Except for the substitution of intermediate A1 in (2) of Synthesis Example 1, the above-mentioned intermediate B1 of the same mol was used instead, and the cyclohexyl propyl chloride was replaced with the same mol of propyl chloride, the rest In all, in the same manner as (2) of Synthesis Example 1, the following intermediate B2 was obtained.

(3) Synthesis of intermediate B3

Except for the replacement of Intermediate A2 in (3) of Synthesis Example 1, the above-mentioned Intermediate B2 of the same mol was used instead, and the silica gel column chromatography was replaced by ethyl acetate: n-hexane (1: The mixed solvent of 6) was subjected to recrystallization, followed by drying and purification. The rest was the same as in Synthesis Example 1 (3), and the following intermediate B3 was obtained.

(4) Synthesis of compound B

Except that in (4) of Synthesis Example 1, the intermediate A3 was substituted and the above-mentioned intermediate B3 of the same mol was used instead, the following compound B was obtained in the same manner as in (4) of Synthesis Example 1.

(Synthesis Example 3: Synthesis of Compound C)

Except that in (2) of Synthesis Example 2, propyl chloride was replaced with butyryl chloride of the same mole, the rest was the same as in Synthesis Example 2, and the following compound C was obtained.

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

Dissolve 0.030 mol of 9H-茀-2-yl-(phenyl) ketone in 45 ml of dichloromethane, cool to -5°C, add anhydrous AlCl ₃ : 0.033 mol, and mix 9 ml of dichloromethane with 0.033 propyl chloride The solution composed of mol is added slowly over 1 hour in a way that the temperature of the reactant will not rise, and stirred at -5°C for 1 hour. Then, the reactant was slowly poured into 250 g of ice water, and after stirring for 30 minutes, the organic layer was separated and washed with 100 ml of distilled water. Next, the recovered organic layer was subjected to vacuum distillation to obtain a product, and recrystallization was performed with 20 ml of a mixed solution of toluene: ethyl acetate (5:1) to obtain the following intermediate D1.

(2) Synthesis of intermediate D2

烷中的(4N)HCl：4.5ml、與亞硝酸異戊酯0.015mol，反應物依25℃攪拌24小時。然後，在反應溶液中添加醋酸乙酯20ml與蒸餾水50ml而萃取有機層。所萃取的有機層利用無水MgSO₄乾燥，將溶劑施行減壓蒸餾而獲得生成物，使用乙醇：醋酸乙酯(5：1)的混合溶劑30ml施行再結晶後，經乾燥，獲得下述中間體D2。 The above intermediate D1 (0.010mol) was dissolved in 30ml of tetrahydrofuran (THF), and dissolved in 1,4-di

(4N) HCl in alkane: 4.5ml, and 0.015mol of isoamyl nitrite, the reactant was stirred at 25°C for 24 hours. Then, 20 ml of ethyl acetate and 50 ml of distilled water were added to the reaction solution to extract the organic layer. The extracted organic layer was dried with anhydrous MgSO ₄ , and the solvent was distilled under reduced pressure to obtain the product. The product was recrystallized using 30 ml of a mixed solvent of ethanol: ethyl acetate (5:1), and dried to obtain the following intermediate D2.

(3) Synthesis of compound D

The above intermediate D2 (0.006mol) was dissolved in 25ml of ethyl acetate under a nitrogen environment, the reactant was maintained at -5°C, and 0.007mmol of triethylamine was added. After stirring the reaction solution for 30 minutes, the reactant did not heat up. Over 30 minutes, slowly add a solution consisting of 0.007 mol of chloroacetate and 5 ml of ethyl acetate, and stir for 30 minutes. Then, 100 ml of distilled water was slowly added to the reactant and stirred for about 30 minutes, and the organic layer was separated. Next, the recovered organic layer was dried with anhydrous MgSO ₄ , and the solvent was subjected to vacuum distillation to obtain the following compound D.

[化23] Compound D

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

In a 500ml four-necked flask, put 0.2mol of diphenyl sulfide, _{0.22mol of powdered AlCl 3} and 150ml of dichloroethane, stir and pour into argon gas, cool to an ice bath, when the temperature drops to 0℃, The solution consisting of 0.22 mol of cyclohexylpropionyl chloride and 42 g of dichloroethane was started to drip, and it was added over about 1.5 hours while adjusting the temperature to 10°C or less. The temperature rose to 15°C, and after stirring for 2 hours, the reaction liquid was discharged.

In dilute hydrochloric acid mixed with ice 400g and concentrated hydrochloric acid 65ml, under stirring, slowly throw into the reaction solution, use a separatory funnel to separate the lower layer, the upper layer is extracted with 50ml dichloroethane, the extract and the lower layer Liquid blending. _{Then, wash with a NaHCO 3} solution blended with NaHCO ₃ : 10g and 200g of water, and then wash with 200ml of water 3 times until the pH is neutral, and then use 60g of anhydrous MgSO _{4 to} dry to remove water before reuse. Rotary evaporation evaporates the dichloroethane. Put the remaining solid powder in the rotary evaporator bottle into 200 ml of petroleum ether, perform suction filtration, and further put in 150 ml of anhydrous alcohol, heat and reflux. Then, it was cooled to room temperature, cooled with ice for 2 hours, suction filtration was performed, and drying was performed in an oven at 50° C. for 2 hours to obtain the following intermediate E1.

[化24] Intermediate E1

(2) Synthesis of Intermediate E2

In a 500ml four-necked flask, put the above intermediate E1: 42g, tetrahydrofuran 400g, concentrated hydrochloric acid 200g and isoamyl nitrite 24.2g, and after stirring at room temperature for 5 hours, the reaction solution was discharged.

The reaction solution was thrown into a large beaker, 1000ml of water was added, and after stirring, it was allowed to stand overnight to separate into layers to obtain a yellow viscous liquid. The viscous liquid was extracted with dichloroethane, poured into 50 g of anhydrous MgSO ₄ and dried, and then subjected to suction filtration. The filtrate was subjected to rotary evaporation to remove the solvent to obtain an oily viscous substance. Next, the viscous substance was thrown into 150 ml of petroleum ether, and after stirring and precipitation, suction filtration was performed to obtain a white powdery solid. Then, it dried at 60 degreeC for 5 hours, and the following intermediate body E2 was obtained.

(3) Synthesis of compound E

In a 1000ml four-necked flask, put the above intermediate E2: 34g, 350ml of dichloroethane and 12.7g of triethylamine, and stir, use an ice bath to cool, when the temperature drops to 0 ℃, start to drip from chlorinated acetic acid A solution composed of 15.7 g and 15 g of dichloroethane was added over about 1.5 hours. Then, after stirring for 1 hour, 500 ml of cold water was dropped, and layering was performed using a separatory funnel. Wash with 200ml of 5% NaHCO ₃ solution once, then wash with 200ml of water twice until the pH is neutral, then wash with dilute hydrochloric acid mixed with 20g of concentrated hydrochloric acid and 400ml of water, and then use After washing with 200 ml of water for 3 times, it was dried with 100 g of anhydrous MgSO ₄ and the solvent was removed by rotary evaporation to obtain a viscous liquid. An appropriate amount of methanol was thrown into the viscous liquid to precipitate a white solid, which was filtered and dried to obtain the following compound E.

(Synthesis Example 6: Synthesis of Compound F)

Except for the substitution of diphenyl sulfide in (1) of Synthesis Example 5, the same mole of [4-(phenylthio)phenyl]-2-thiophene-methanone was used instead, and the rest were all synthesized in accordance with Example 5 The following compound F was synthesized in the same manner.

[化27] Compound F

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

In a 500 mL round-bottomed four-neck separable flask equipped with a cooling tube, addition funnel, nitrogen inlet pipe, mechanical stirrer, and digital thermometer, add THF: 250 parts by mass and 0.6 parts by mass of lithium chloride, sufficient Implement nitrogen substitution. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Dropped in an addition funnel over 60 minutes: 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 methyl methacrylate (MMA) 17.5 parts by mass. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was dropped over 20 minutes. After 30 minutes of reaction, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was re-precipitated in hexane, filtered and vacuum dried for purification, and diluted with PGMEA to become a solid content 30% by mass solution. 32.5 parts by mass of water was added, the temperature was raised to 100°C, and the reaction was carried out for 7 hours to deprotect the structural unit derived from EEMA to become a structural unit derived from methacrylic acid (MAA). The obtained block copolymer PGMEA solution was re-precipitated in hexane, filtered and vacuum-dried for purification to obtain an A block containing the structural unit represented by general formula (I) and a structural unit derived from a carboxyl-containing monomer And has a solvent-philic B block block copolymer A (acid value 8mgKOH/g, Tg38℃). The block copolymer A thus obtained was confirmed by GPC (Gel Permeation Chromatography Analyzer). As a result, the weight average molecular weight Mw was 7730. In addition, the amine value is 95 mgKOH/g.

(Synthesis Example 8: Synthesis of Alkali-soluble Resin A Solution)

A mixture 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 dropped onto the polymerized PGMEA: 150 parts by mass at 100°C for 3 hours under nitrogen flow. Slot. After the dropping is finished, heating is further performed at 100°C for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution is 7,000.

Next, add 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol to the obtained polymer solution, and heat at 110°C for 10 hours. Air bubbles in the solution. The obtained alkali-soluble resin A is based on the main chain formed by the copolymerization of styrene MMA and MAA. GMA is used to introduce a resin with side chains of ethylenic double bonds. The solid content is 42.6% by mass and the acid value is 74mgKOH/g. , The weight average molecular weight is 12,000. Using polystyrene as the standard substance and THF as the eluent, the weight average molecular weight was measured using Shodex GPC System-21H. In addition, the acid value measurement method is based on JIS K 0070.

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

With reference to the manufacturing method of Intermediate 3 and Intermediate 4 described in International Publication No. 2012/144521, Intermediate 1: 15.9 g (yield 70%) represented by the following chemical formula (1) was obtained.

The obtained compound was confirmed to belong to the target compound through the following analysis results.

‧MS(ESI)(m/z): 511(+), 2 price

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

(2) Synthesis of blue color material α

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

The obtained compound was confirmed to belong to the target compound through the following analysis results.

‧MS(ESI)(m/z): 510(+), 2 price

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

(Synthesis Example 10: Preparation of Azo Derivative 1)

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

(Synthesis Example 11: Preparation of Azo Derivative 2)

Except in the preparation of Azo derivative 1 of Synthesis Example 10, instead of 0.39 mol nickel chloride solution and 0.21 mol zinc chloride solution, 0.42 mol nickel chloride solution and 0.18 mol zinc chloride solution were used instead Other than that, in the same manner as in Synthesis Example 10, Azo derivative 2 (Ni-azo-2, Ni:Zn=70:30 (mole ratio) azo pigment) was obtained.

(Synthesis Example 12: Preparation of Azo Derivative 3)

Except in the preparation of Azo derivative 1 of Synthesis Example 10, instead of 0.39 mol nickel chloride solution and 0.21 mol zinc chloride solution, 0.3 mol nickel chloride solution and 0.3 mol zinc chloride solution were used instead Other than that, in the same manner as in Synthesis Example 10, Azo derivative 3 (Ni-azo-3, Ni:Zn=50:50 (mole ratio) azo pigment) was obtained.

(Synthesis Example 13: Preparation of Azo Derivative 4)

Except in the preparation of Azo derivative 1 of Synthesis Example 10, instead of 0.39 mol nickel chloride solution and 0.21 mol zinc chloride solution, 0.18 mol nickel chloride solution and 0.42 mol zinc chloride solution were used instead Other than that, in the same manner as in Synthesis Example 10, Azo derivative 4 (Ni-azo-4, Ni:Zn=30:70 (mole ratio) azo pigment) was obtained.

(Synthesis Example 14: Preparation of Azo Derivative 5)

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

(Synthesis Example 15: Synthesis of Potential Antioxidant (Compound a))

Mix 0.01 mol of the phenol compound represented by the following chemical formula (3), 0.05 mol of di-tert-butyl dicarbonate, and 30 g of pyridine. In a nitrogen environment, add 0.025 mol of 4-dimethylaminopyridine at room temperature to 60 Stir at °C for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added to perform oil-water separation. After the organic layer was dried with anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue to perform crystallization. The obtained white powdery crystals were dried under reduced pressure at 60°C for 3 hours to obtain the potential antioxidant (compound a) represented by the above chemical formula (a). In addition, the structure of the obtained potential antioxidant was confirmed by IR and NMR.

(Example 1) (1) Manufacturing of color material dispersion liquid 1

The block copolymer A of Synthesis Example 7 of the dispersant: 5.1 parts by mass, the blue color material α obtained in Synthesis Example 9 of the color material: 13.0 parts by mass, and the alkali-soluble resin A solution obtained in Synthesis Example 8 were converted into solid content. 5.1 parts by mass, PGMEA: 76.8 parts by mass, and 100 parts by mass of zirconia beads with a particle size of 2.0mm, put them in a beauty milk bottle, and use a paint stirrer (manufactured by Asada Iron Works Co., Ltd.) for 1 hour shaking Pre-crushing, then take out the zirconia beads with a diameter of 2.0mm, add 200 parts by mass of zirconia beads with a diameter of 0.1mm, and perform the formal crushing for 4 hours with a paint stirrer to obtain a color material dispersion. 1.

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

Addition: 1:286.1 parts by mass of the color material dispersion 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, photopolymerizable compound (trade name Aronix M-520D, East Asia Synthetic Co., Ltd.) 18.2 parts by mass, dibutylhydroxytoluene (BHT) as antioxidant: 2.0 parts by mass, compound A obtained in Synthesis Example 1 of the first initiator: 5.1 parts by mass and PGMEA: 42.2 parts by mass, The photosensitive colored resin composition 1 for color filters was obtained.

(Examples 2~13)

In Example 1, except that the type and amount shown in Table 1 were used for the photoinitiator system, in the same manner as in Example 1, photosensitive colored resin compositions 2 to 13 for color filters were obtained.

In addition, the OXE-01-based oxime ester-based photoinitiator (trade name IRGACURE OXE-01, manufactured by BASF) used as the photoinitiator in Example 8 is a compound represented by the following chemical formula (4): [formula 31 ]

(Example 14)

Except that in Example 13, BHT was not used as the antioxidant system, and bisphenol-based antioxidant (ADEKA STAB AO-40, manufactured by ADEKA) was used instead, and the rest were followed in the same manner as in Example 13 to obtain a photosensitive color filter.性colored resin composition 14.

(Example 15)

Except that in Example 13, BHT was not used for the antioxidant system, and a hindered phenol-based antioxidant (Irg1010, manufactured by BASF) was used instead, and the rest were followed in the same manner as in Example 13 to obtain a photosensitive colored resin composition for color filters 15.

(Example 16)

Except that in Example 13, the antioxidant system does not use BHT, and instead uses compound a, which is a potential antioxidant obtained in Synthesis Example 15, the photosensitive coloring for color filters is obtained in the same manner as in Example 13. Resin composition 16.

(Examples 17-21)

Except that in Example 1, the addition amounts of the alkali-soluble resin, photopolymerizable compound, photoinitiator, and antioxidant were changed as shown in Table 1, the color filters were obtained in the same manner as in Example 1. Photosensitive colored resin compositions for sheets 17-21.

(Comparative Examples 1~3)

Except that in Example 21, the photoinitiator system did not use the compound A obtained in Synthesis Example 1, and instead used the photoinitiator shown in Table 1, the rest were the same as in Example 21 to obtain a comparative color filter. Use photosensitive colored resin composition 1 to 3.

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

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

(Example 22)

In Example 13, except that the color material was substituted for the blue color material α, and 37.2 parts by mass of Pigment Red 254 (PR254) was used instead, the rest were the same as in Example 13 to obtain photosensitive coloring for color filters. Resin composition 22.

(Comparative Example 4)

In Example 22, the photo-initiating agent did not use the compound A obtained in Synthesis Example 1, the compound E obtained in Synthesis Example 5, and Irg819 (manufactured by BASF), but the amount shown in Table 2 was used in the above-mentioned chemical formula (5). OXE-02 (manufactured by BASF) is shown, and no antioxidant (BHT) is used, and 20.2 parts by mass of a photopolymerizable compound is used instead, and the rest are the same as in Example 22 to obtain a photosensitive coloring for a comparative color filter Resin composition 4.

(Example 23)

In Example 13, except that the color material system replaced the blue color material α, used Pigment Green 59 (PG59) 16.48 parts by mass and 1:20.72 parts by mass of the Azo derivative obtained in Synthesis Example 10, the rest were all in accordance with In Example 13, a photosensitive colored resin composition 23 for color filters was obtained in the same manner.

(Comparative Example 5)

Except in Example 23, the photoinitiator did not use the compound A obtained in Synthesis Example 1, the compound E obtained in Synthesis Example 5, and Irg819 (manufactured by BASF). OXE-02 (manufactured by BASF) is shown, and no antioxidant (BHT) is used, and 20.2 parts by mass of a photopolymerizable compound is used instead. The rest are the same as in Example 23 to obtain a photosensitive coloring for a comparative color filter Resin composition 5.

(Example 24)

Except in Example 13, the color material system replaced the blue color material α, instead of using CI Solvent Yellow 162: 37.2 parts by mass, and not using antioxidants (BHT), instead of using 20.2 parts by mass of photopolymerizable compounds , And the rest is the same as in Example 13 to obtain a photosensitive colored resin composition 24 for color filters.

(Comparative Example 6)

Except in Example 24, the photoinitiator did not use the compound A obtained in Synthesis Example 1, the compound E obtained in Synthesis Example 5, and Irg819 (manufactured by BASF), but the amount shown in Table 2 was used in the above chemical formula (5). In the same manner as in Example 24, except for OXE-02 (manufactured by BASF), a photosensitive colored resin composition 6 for a comparative color filter was obtained.

(Example 25)

Except that in Example 16, the color material system replaced the blue color material α, and replaced it with pigment green 58: 23.8 parts by mass and 2: 13.4 parts by mass of the Azo derivative obtained in Synthesis Example 11. In Example 16, a photosensitive colored resin composition 25 for color filters was obtained in the same manner.

(Example 26)

Except that in Example 16, the color material system replaced the blue color material α, and instead used pigment green 58: 24.5 parts by mass and the Azo derivative obtained in Synthesis Example 12: 12.7 parts by mass, the rest were all in accordance with Example 16. In the same manner, a photosensitive colored resin composition 26 for color filters was obtained.

(Example 27)

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

(Example 28)

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

(Example 29)

In Example 27, except that the antioxidant system replaced compound a and BHT was used, the photosensitive colored resin composition 29 for a color filter was obtained in the same manner as in Example 27.

(Example 30)

Except that in Example 27, the antioxidant compound a was not used, but 20.2 parts by mass of the photopolymerizable compound was used. In the same manner as in Example 27, a photosensitive colored resin composition for color filters was obtained. 30.

(Comparative Example 7)

Except in Example 27, the photoinitiator did not use the compound A obtained in Synthesis Example 1, the compound E obtained in Synthesis Example 5, and Irg819 (manufactured by BASF), but the amount shown in Table 2 was used in the above-mentioned chemical formula (5). OXE-02 (manufactured by BASF) is shown, and no antioxidant is used, and 20.2 parts by mass of a photopolymerizable compound is used instead. The rest are the same as in Example 27 to obtain a photosensitive colored resin composition for a comparative color filter 7.

[Evaluation]

The photosensitive colored resin composition obtained in each example and each comparative example was applied on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater so that the cured coating film had a thickness of 3.0 μm. After coating, using a hot plate, drying was performed at 80°C for 3 minutes to form a coating film on the glass substrate. For the coating film, a patterned mask (chrome mask) with a 20μm×20μm chrome mask placed in the center of an independent thin line with an opening size of 90μm×300μm was ^{exposed using an ultra-high pressure mercury lamp under 40mJ/cm 2} ultraviolet rays. , And a post-exposure coating film is formed on the glass substrate. Next, a 0.05wt% potassium hydroxide aqueous solution was used as the developer, and spin-coated development was performed. After being in contact with the developer for 60 seconds, it was rinsed with pure water and then subjected to a development process to obtain an independent fine-line patterned coating film with micropores. . Then, it was post-baked in a 230°C dust-free oven for 25 minutes to form an independent fine-line pattern-like colored layer with minute holes. The following evaluation was performed on the obtained colored layer.

<Evaluation of Optical Properties>

The photosensitive colored resin composition obtained in each example and each comparative example was coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater, and then a hot plate was used to apply 80 It was dried at °C for 3 minutes to form a coating film on the glass substrate. Without intervening the photomask, an ultra-high pressure mercury lamp was used to irradiate 60 mJ/cm ^{2 of} ultraviolet rays on the entire surface to form a post-exposure coating film. Next, a 0.05 wt% potassium hydroxide aqueous solution was used as a developer, and spin-coating development was performed. After being in contact with the developer for 60 seconds, it was washed with pure water and subjected to a development process to form a post-development coating film. Then, post-bake in a dust-free oven at 230℃ for 25 minutes. When using blue color material α, it becomes y=0.083, and when using PR254, it becomes x=0.650. When using PG59/Azo When it is derivative, it becomes y=0.610, when CI solvent yellow 162 is used, it becomes y=0.503, and when PG58/Azo derivative is used, it becomes y=0.630 to form a hardened coating (coloring layer). The chromaticity (x, y) and luminance (Y) of the colored layer were measured using a microscope OSP-SP200 manufactured by Olympus.

<Developability Evaluation> [Straightness]

For the thin line pattern width of the colored layer of the chrome mask used during exposure with an opening width of 90μm, the width of the colored layer was measured at 5 places with an optical microscope, and the linearity was evaluated based on the variation of the line width.

A: The variation is within ±0.1μm

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

C: Variation exceeds ±0.3μm

[Residual film rate]

When the colored layer is formed, in the coating film formation process, the film thickness after exposure (E) and the film thickness after development (D) are measured with a stylus profiler P-16 (manufactured by KLA-Tencor). The film thickness after development (D)/the film thickness after exposure (E) was calculated as the residual film rate.

In addition, if the film thickness after development (D)/the film thickness after exposure (E) is more than 90%, it belongs to the range suitable for practical use.

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

[Shape]

A: Relative to the size of the chrome mask arranged in the independent thin line pattern, the size deviation of the micro holes formed in the colored layer is less than 2% in absolute value

B: Relative to the size of the chrome mask arranged in the independent thin line pattern, the size deviation of the micro holes formed in the colored layer is 2% or more and less than 6% in absolute value

C: Relative to the size of the chrome mask arranged in the independent thin line pattern, the size deviation of the micro holes formed in the colored layer is greater than 6% and less than 8% in absolute value

D: Relative to the size of the chrome mask arranged in the independent thin line pattern, the size deviation of the micro holes formed in the colored layer is greater than 8% in absolute value

In addition, the size deviation system calculates the average value of the size deviation of each side.

[Trembling]

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

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

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

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

[Development residue]

AA: When observed with an optical microscope, no coloring was observed inside the micropores formed in the colored layer, and no transparent matter was observed at the periphery of the micropores.

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

B: During observation with an optical microscope, coloration is observed in the inside of the micropores formed in the colored layer

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

‧OXE-01: Oxime ester-based photoinitiator (trade name IRGACURE OXE-01, manufactured by BASF)

‧OXE-02: Oxime ester-based photoinitiator (trade name IRGACURE OXE-02, manufactured by BASF)

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

‧Irg907: α-aminoketone-based photoinitiator (IRGACURE 907, manufactured by BASF)

‧Sulfhydryl series: Sulfhydryl chain transfer agent (2-mercaptobenzothiazole, manufactured by Tokyo Chemical Industry)

‧Diimidazole series: Diimidazole series photoinitiator (manufactured by HABI, Black Gold Chemicals)

系光起始劑(DOUBLECURE DETX、Double BondChemical製) ‧DETX: Oxygen Sulfur

Photoinitiator (DOUBLECURE DETX, Double Bond Chemical product)

‧Irg819: Phosphine oxide-based photoinitiator (IRGACURE 819, manufactured by BASF

‧BHT: dibutyl hydroxytoluene

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

‧Irg1010: hindered phenol antioxidant (IRGACURE 1010, made by BASF)

<Results collation>

The photoinitiator is the photosensitive colored resin composition of Examples 1 to 30 containing the oxime ester compound represented by the above general formula (1). Compared with the comparative photosensitive colored resin composition using the same color materials, It is known that a colored layer with enhanced brightness can be formed. In addition, the colored resin composition system of Examples 1 to 30 has a high residual film rate and good sensitivity. The photosensitive colored resin composition of Examples 1 to 30 is known to have excellent linearity of the fine line pattern, and when the colored layer is patterned, the desired minute holes can be easily formed in the colored layer at the same time. In addition, Examples 1 to 3 using the oxime ester compound in which Z in the above general formula (1) is a hydrogen atom are high in brightness and residual film rate; Z in the above general formula (1) is -(C=O) Example 4 of the oxime ester compound of R ^d is that the oxime ester compound has better solvent solubility and compatibility with other components, and the shape of the micropores is better. Observation and comparison of the cross-sections of the micro-holes of Example 1 and Example 2 show that the pull-out angle of Example 2 is gentler, and the shape of the micro-holes is better.

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

系光起始劑、醯化膦氧化物系光起始劑與巰系鏈轉移劑中選擇之至少1種，則細線圖案的直線性獲提升，且微小孔的形狀更良好(實施例5與實施例9~13的比較)。 Furthermore, the photoinitiator system uses a combination of the oxime ester compound represented by the above general formula (1) and the oxime ester compound having a diphenyl sulfide skeleton, and further contains a photoinitiator from the α-amine ketone system and the diimidazole system. Photoinitiator, oxygen sulfur

Based on at least one of the photoinitiator, phosphine oxide photoinitiator, and sulfhydryl chain transfer agent, the linearity of the fine line pattern is improved, and the shape of the micropores is better (Example 5 and Comparison of Examples 9-13).

Furthermore, by containing antioxidants, the tremor of the micropores is further suppressed, and the brightness is also improved (comparison between Example 1 and Example 21, and comparison between Examples 27 and 29 and Example 30). When a latent antioxidant (compound a) is used from the antioxidant system, the shaking of the micropores can be more suppressed, and the residual film rate is as good as the case where no antioxidant is used. On the other hand, when the latent antioxidant is not used but a hindered phenol antioxidant is used, the brightness can be improved more than the case of using the latent antioxidant (comparison between Examples 27 and 29 and Example 30).

On the other hand, the photoinitiator does not contain the oxime ester compound represented by the above general formula (1), but uses the oxime ester compound with a carbazole skeleton in Comparative Example 1 and Comparative Examples 4 to 7, compared to the use of the same In the example of the color material, the brightness is poor, the linearity of the thin line pattern is poor, and the minute holes cannot be formed.

Furthermore, the photoinitiator did not contain the oxime ester compound represented by the above general formula (1), but in Comparative Example 2 using Irg907 (α-amine ketone-based photoinitiator), both brightness and residual film rate were poor.

The photoinitiator does not contain the oxime ester compound represented by the above general formula (1), but uses the comparative compound A with a nitro group in the stilbene skeleton and the oxime ester group is not bonded to the stilbene skeleton by a carbonyl group. 3. Both brightness and linearity are poor. The reason for the poor linearity of Comparative Example 3 is presumed to be due to the poor solvent solubility of Comparative Compound A and poor compatibility with other components.

Claims (10)

A photosensitive colored resin composition for color filters, which contains: color material, alkali-soluble resin, photopolymerizable compound, photoinitiator and solvent; the photoinitiator contains the following general formula (1) Shows an oxime ester compound; further containing an antioxidant, the antioxidant is at least one selected from the group consisting of hindered phenolic antioxidants and potential hindered phenolic antioxidants; the potential hindered phenolic antioxidants are based on The phenolic hydroxyl group of the hindered phenol antioxidant is protected by the protective group that can be removed by heating;

(In general formula (1), R ^a and R ^b are each independently a hydrogen atom or an alkyl group; R ^c may also contain thioether bonds (-S-), ether bonds (-O-), and carbonyl bonds ( -CO-) is a hydrocarbon group of at least one bivalent linking group; Z is a hydrogen atom or -(C=O)R ^d ; R ^d may also contain at least one selected from an oxygen atom and a sulfur atom hydrocarbon group, a nitrogen atom or not, and containing at least one kind of selected heterocyclic group from an oxygen atom and a sulfur atom; R ^e based carbon number of the hydrocarbon group having 1 to 10). The photosensitive colored resin composition for color filters according to claim 1, wherein the photoinitiator contains two or more types of oxime ester compounds that do not have a carbazole skeleton. Such as claim 1 or 2 of the photosensitive colored resin composition for color filters, which Among them, the photoinitiator system further contains an oxime ester compound having a diphenyl sulfide skeleton. According to claim 1 or 2, the photosensitive colored resin composition for color filters, wherein the photoinitiator system further contains a photoinitiator from an α-amine ketone-based photoinitiator, a biimidazole-based photoinitiator Agent, oxygen and sulfur

At least one selected from photoinitiator, phosphine oxide photoinitiator and sulfhydryl chain transfer agent. According to claim 1, the photosensitive colored resin composition for color filters, wherein the photoinitiator system further contains: a

At least one selected from a photoinitiator, a phosphine oxide photoinitiator, and a mercapto-based chain transfer agent; and an oxime ester compound with a diphenyl sulfide skeleton. The photosensitive colored resin composition for color filters according to claim 1, which further contains a dispersant, the dispersant system contains a polymer, and the polymer has a structure represented by the following general formula (I) and has an amine value Above 40mgKOH/g and below 120mgKOH/g:

(In general formula (I), R ¹ is a hydrogen atom or a methyl group; Q is a direct bond or a divalent linking group; R ² is an alkylene group with 1 to 8 carbon atoms, -[CH(R ⁵ )-CH (R ⁶ )-O] _x -CH(R ⁵ )-CH(R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -as indicated by the divalent organic group; R ³ And R ⁴ are each independently a chain or cyclic hydrocarbon group that may be substituted, or R ³ and R ⁴ are bonded to each other to form a cyclic structure; R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group; x is An integer from 1 to 18; y is an integer from 1 to 5; z is an integer from 1 to 18). The photosensitive colored resin composition for a color filter according to claim 6, wherein the dispersant contains a polymer having a structure represented by the general formula (I) and an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less , And the acid value is 1 mgKOH/g or more and 18 mgKOH/g or less. According to claim 1 or 6, the photosensitive colored resin composition for color filters, wherein the color material contains zinc phthalocyanine pigment and a yellow color material; the yellow color material contains: from the following general formula (ii) At least one anion selected from the group consisting of mono-, di-, tri-, and tetra-anions of the azo compound and its tautomeric structure of the azo compound, and at least one anion selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, At least two metal ions selected from the group consisting of Zn, Fe, Ni, Cu and Mn;

(In the above general formula (ii), R ³¹ is each independently OH, NH ₂ , NH-CN, acylated amino, alkylamino, or arylamino; R ³² is each independently -OH or- NH ₂ ). A color filter comprising at least a substrate and a coloring layer provided on the substrate; at least one of the coloring layers is a photosensitive coloring resin composition for color filters according to any one of claims 1 to 8 The colored layer formed by the hardened material. A display device is provided with the color filter of claim 9.

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