TWI774993B - Coloring resin composition, and color filter and display device using the same - Google Patents

Abstract

Embodiments of the present disclosure provide a coloring resin composition, and a color filter and a display device using the same.　The coloring resin composition includes a colorant, a resin, a photo-polymerizable monomer, a photo initiator and a solvent. The resin includes epoxy dicyclopentenyl monomer units and silicon alkyl monomer units.

Description

Colored resin composition, color filter and display device using the same

The present disclosure relates to a colored resin composition. The present disclosure also relates to a color filter formed from the colored resin composition. The present disclosure also relates to a display device including the color filter.

In displays, color filters are commonly used to control the color of each pixel. For example, in earlier liquid crystal displays, color filters were formed on a substrate opposite to a thin film transistor substrate, and the overall structure of the substrate and the color filters disposed thereon was often referred to as a color filter. Optical substrate. The photoresist structure of the color filter can be formed using the resin composition.

In general, for various types of display applications, the composition of the colored resin composition can be adjusted and optimized to form various color filters with predetermined characteristics.

The present disclosure relates to a colored resin composition, a color filter using the same, and a display device. The resin of the coloring resin composition of the embodiment contains epoxy dicyclopentenyl (EDCP) monomer units, which can effectively reduce the degree of thermal shrinkage of the coating of the coloring resin composition when subjected to a high temperature process, and reduce the composition of the coloring resin. The coating of the material is deformed due to the high temperature process, so that the subsequent material coating can still be well attached to the coating of the colored resin composition even after the high temperature process, so the heat resistance and stability of the overall structure can be improved.

According to an embodiment of the present disclosure, a colored resin composition is provided. The colored resin composition contains a colorant, a resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. The aforementioned resin contains epoxy dicyclopentenyl (EDCP) monomer units and silane-based monomer units.

According to another embodiment of the present disclosure, a color filter is provided. This color filter is formed of, for example, the aforementioned colored resin composition.

According to a further embodiment of the present disclosure, a display device is provided. The display device includes, for example, the aforementioned color filter.

In the embodiments of the present disclosure, the resin of the colored resin composition contains epoxy dicyclopentenyl (EDCP) monomer units, which can effectively reduce the degree of thermal shrinkage of the coating of the colored resin composition when subjected to a high temperature process , reduce the deformation of the coating of the colored resin composition due to the high temperature process, so that the subsequent material coating can still be well attached to the coating of the colored resin composition even after the high temperature process, so it can improve the heat resistance and heat resistance of the overall structure. stability. Various embodiments are provided below for detailed description. The embodiments are only used as examples to illustrate, and do not limit the scope of protection of the present disclosure. The present disclosure can still be implemented by adopting other features, elements, methods and parameters. The embodiments are provided only to illustrate the technical features of the present disclosure, and are not intended to limit the scope of the patent application of the present disclosure. Those with ordinary knowledge in the technical field can make equivalent modifications and changes according to the description of the following specification without departing from the spirit and scope of the present disclosure.

Some embodiments of the present disclosure relate to a pigmented resin composition. Such a colored resin composition contains a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E). The resin (B) contains epoxy dicyclopentenyl monomer units and silyl monomer units.

Here, the terms of the colorant (A), resin (B), photopolymerizable monomer (C), photopolymerization initiator (D), solvent (E) and other components may independently include a single one or a plurality of In the case of the components such as colorant (A), resin (B), photopolymerizable monomer (C), photopolymerization initiator (D), and solvent (E).

In the manufacturing process of the display device, after the coating and developing process of the color photoresist is completed, it is necessary to continue to coat a plurality of other material layers on the color photoresist, and multiple high temperature processes (for example, 220° C. ~250°C) to bake these layers of material to dry and adhere to the color photoresist. However, the color photoresist is prone to shrink in volume during the high-temperature baking process, which may lead to poor adhesion between the material layer and the color photoresist.

According to an embodiment of the present disclosure, the resin (B) includes the resin (B-1), and the resin (B-1) includes epoxy dicyclopentenyl (EDCP) monomer units, which can effectively reduce the coloring resin composition The thermal shrinkage of the coating of the material during the high temperature process reduces the deformation of the coating of the colored resin composition due to the high temperature process, so that the subsequent material coating can still be well adhered to the coating of the colored resin composition even after the high temperature process. layer, so the heat resistance and stability of the overall structure can be improved.

Specifically, according to the embodiments of the present disclosure, the epoxydicyclopentenyl monomer unit has a three-dimensional structure, which can improve the strength of the cross-linked polymer network of the resin, so that the structure of the colored resin composition is relatively stable Therefore, the coating is less likely to be decomposed or shrunk by heat, so the heat resistance stability of the coating of the colored resin composition can be improved.

Furthermore, according to the embodiment of the present disclosure, the resin (B) further includes the resin (B-2), the resin (B-2) includes a silane-based monomer unit, and the silicon atom in the silane-based monomer unit is relatively high. The carbon atoms in the molecular structure have a larger size and form a longer bond length, so the silane-based monomer unit in the resin (B) and the epoxy dicyclopentenyl monomer unit can further help reduce heat exposure. The volume shrinkage at the time, and help to improve the heat resistance and stability of the overall structure.

In some embodiments, colorant (A) may comprise pigments and dyes. According to some embodiments, the pigment of the colorant (A) is not particularly limited, and well-known pigments can be used, for example, compounds classified as pigments in the color index (published by The Society of Dyers and Colourists) can be exemplified. According to some embodiments, the dye of the colorant (A) is not particularly limited as long as it can be appropriately selected in accordance with the desired spectral spectrum of the color filter. In some embodiments, the dye may preferably be an oxonone dye.

In some embodiments, the colorant (A) may account for, for example, more than 3 wt % of the colored resin composition. In some embodiments, the colorant (A) may account for, for example, 4 wt % to 10 wt % of the colored resin composition. In some embodiments, the dye may comprise about 1-100 wt% of the colorant (A), preferably about 5-95 wt%.

In some embodiments, the colorant (A) may include a first colorant, and the first colorant is a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)).

In formula (I), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon group which may have a substituent group. The aralkyl group of numbers 7 to 30, the aromatic hydrocarbon group and the substituent that the aralkyl group may have can be -SO ₃ - or -SO ₂ -N ^- -SO ₂ -R ^f , and the saturated hydrocarbon group contains The hydrogen atoms can be substituted or unsubstituted amine groups or halogen atoms. When the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not substituted with -O- at the same time, and the terminal -CH ₂ - is not substituted with -O- or -CO-. R ⁴¹ and R ⁴² may form a bond and form a ring together with the nitrogen atom to which the R ⁴¹ and R ⁴² are bonded, and R ⁴³ and R ⁴⁴ may bond and bond with the R ⁴³ and R ⁴⁴ The nitrogen atoms together form a ring.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f or an alkyl group having 1 to 8 carbon atoms, constituting the -CH ₂ - of the alkyl group can be replaced by at least one of -O- and -CO-, R ⁴⁸ and R ⁵² can be bonded to each other to form -NH-, -S- or -SO ₂ -, but In this alkyl group, the adjacent -CH ₂ - is not substituted with -O- at the same time, and the terminal -CH ₂ - is not substituted with -O- or -CO-.

Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, or a carbon number that may have a substituent The aromatic hydrocarbon group of 6 to 20, which may have a substituent including -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

M ^r+ is hydrogen ion, r-valent metal ion or substituted or unsubstituted ammonium ion; k is the number of -SO ₃ ^- possessed by R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ The sum of -SO ₂ -N ^- -SO ₂ -R ^f ; r represents an integer of 1 or more. R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms, except that R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

The aromatic heterocyclic ring represented by ring T ¹ may be a monocyclic ring or a condensed ring. The carbon number of the aromatic heterocyclic ring represented by ring T ¹ is 3 to 10, preferably 3 to 8. In addition, the aromatic heterocycle is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. Examples of monocyclic aromatic heterocycles include five-membered rings containing nitrogen atoms such as pyrrole rings, pyrazole rings, imidazole rings, and thiazole rings; five-membered rings containing no nitrogen atoms such as furan rings and thiophene rings; pyridine A 6-membered ring containing a nitrogen atom such as a ring, a pyrimidine ring, and the like, and the condensed aromatic heterocyclic ring includes a condensed ring containing a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring. ; Condensed rings that do not contain nitrogen atoms such as benzofuran rings, etc.

As a substituent which the aromatic heterocycle of ring T ¹ may have, a halogen atom, a cyano group, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group, or a substituted or unsubstituted amine group may be exemplified. Aromatic hydrocarbon group having 6 to 20 carbon atoms, etc., preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, or an optionally substituted group having 6 to 20 carbon atoms of aromatic hydrocarbons. Ring T ¹ preferably has an amine group which may have a substituent, and the substituent which the amine group may have is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, Aralkyl and the like having 7 to 30 carbon atoms of the substituent.

In some embodiments, the aromatic heterocycle of the ring T ¹ may be an aromatic heterocycle containing a nitrogen atom, more preferably a 5-membered aromatic heterocycle containing a nitrogen atom.

(t1)In some embodiments, ring T1 may be ^a ring as represented by formula (t1).

(t1)

In formula (t1), R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. X2 represents -O-, -N(R ⁵⁷ )- or -S-, and R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted carbon number 7 In the aralkyl group of to 30, when the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not substituted with -O- at the same time, and the terminal -CH ₂ - is not substituted with -O- or -CO-. R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which the R ⁴⁵ and R ⁴⁶ are bonded. * represents the bonding position with the carbocation in formula (I).

(t2)In some embodiments, ring T ¹ can also be a ring as represented by formula (t2).

(t2)

In formula (t2), ring T ³ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms having a nitrogen atom; R ⁵⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms which may have a substituent family hydrocarbon group, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ; R ⁵⁹ represents a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbon atoms which may have a substituent, a group with 6 carbon atoms which may have a substituent An aromatic hydrocarbon group of to 20 or an aralkyl group of 7 to 30 carbon atoms which may have a substituent; k2 represents 0 or 1; * represents a bond terminal to the carbocation in the formula (I).

(t2-1)In some embodiments, ring T ¹ may be a ring as represented by formula (t2-1).

(t2-1)

In formula (t2-1), R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. R ⁶¹ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . R ⁵⁹ is synonymous with R ⁵⁹ in the aforementioned formula (t2). * denotes the bond terminal to the carbocation in formula (I).

Among the saturated hydrocarbon groups with 1 to 20 carbon atoms among R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ , and the amine groups that may be substituted for ring T ¹ , the saturated hydrocarbon groups with 1 to 20 carbon atoms may have, which Any of linear, branched and cyclic may be used. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, Straight-chain alkyl groups such as hexadecyl and eicosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The carbon number of the saturated hydrocarbon group may be 1 to 10, more preferably 1 to 8, further preferably 1 to 6.

The cyclic saturated hydrocarbon group among R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the amine group that ring T ¹ may have, the cyclic saturated hydrocarbon group that may have, may be monocyclic or polycyclic . Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon group may be 3 to 10, preferably 6 to 10.

The saturated hydrocarbon group among R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ , and the saturated hydrocarbon group that the ring T ¹ may have on the amine group may have a substituted or unsubstituted amine group or a halogen atoms as substituents. Examples of the substituted amino group include alkylamino groups such as a dimethylamino group and a diethylamino group. Moreover, fluorine, chlorine, bromine, and iodine are mentioned as a halogen atom. When the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as trifluoromethyl, perfluoroethyl, and perfluoropropyl.

The alkyl group with 1 to 8 carbon atoms in R ⁴⁷ to R ⁵⁴ may be a saturated hydrocarbon group with a carbon number of 1 to 8 among the linear or branched saturated hydrocarbon groups exemplified by the saturated hydrocarbon group in the aforementioned R ⁴¹ Hydrocarbyl.

In addition, the alkyl group having 1 to 10 carbon atoms in R ⁵⁷ may be a saturated hydrocarbon group having 1 to 10 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group in the aforementioned R ⁴¹ . .

When the carbon number of the saturated hydrocarbon group in R ⁴¹ to R ⁴⁶ is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted with -O-, and the terminal -CH ₂ - is not substituted with -O- or -CO-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (that is, a linear like alkyl). The preferred carbon number of the saturated hydrocarbon group in which -CH ₂ - may be substituted with at least one of -O- and -CO- is 2 to 10, more preferably 2 to 8. In addition, when -CH ₂ - is substituted with at least one of -O- and -CO-, between the terminal and -O- or -CO-, or between -O- or -CO- and -O- or - The carbon number between CO- is 1 or more, or may be 1 to 5, preferably 2 to 3.

In addition, the aromatic hydrocarbon group which may have a substituent among R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ and the substituted amine group which the ring T ¹ may have, the aromatic hydrocarbon group (wherein , the aromatic hydrocarbon group may have a substituent) preferably has a carbon number of 6 to 20, or may be 6 to 15, or may be 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, and a phenyl group, a naphthyl group, a tolyl group, and a xylene group are preferred base. In addition, the aromatic hydrocarbon group may have one or two or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; halogenated alkyl groups having 1 to 6 carbon atoms such as chloromethyl group and trifluoromethyl group; carbon atoms such as methoxy group and ethoxy group. Alkoxy of 1 to 6; hydroxyl; sulfasulfonyl; alkylsulfonyl of 1 to 6 carbons such as methylsulfonyl; methoxycarbonyl, ethoxycarbonyl and other carbons of 1 to 6 Alkoxycarbonyl; -SO ₃ ^- ; -SO ₂ -N ^- -SO ₂ -R ^f , etc., may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . In some embodiments, ^-SO3- and _{-SO2 -} N ^-- SO2 _- ^Rf are directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, replace the hydrogen atom bonded to the aromatic hydrocarbon ring .

As a specific example of the aromatic hydrocarbon group which may have a substituent, the group represented by the following formula is mentioned, for example. In the following formula, * represents a bond terminal with a nitrogen atom.

The aralkyl group that may have a substituent in R ⁴¹ to R ⁴⁶ and R ⁵⁹ , and the substituted amine group that may have in the ring T ¹ , the aralkyl group (wherein the aralkyl group may have Substituents), such as methylene group, ethylidene group, propylidene group, etc. C1 to 10 (preferably C1 to 5) alkylene group bonded to the above-mentioned aromatic hydrocarbon group. group, etc. The carbon number of the aralkyl group may be 7 to 30, or 7 to 20, or may be 7 to 17 carbon atoms.

R ⁴¹ and R ⁴² are bound together and form a ring together with the nitrogen atom to which R ⁴¹ and R ⁴² are bound, and R ⁴³ and R ⁴⁴ are bound to the nitrogen atom to which the R ⁴³ and R ⁴⁴ are bound The ring formed together and the ring formed by R ⁴⁵ and R ⁴⁶ are bonded together with the nitrogen atom to which R ⁴⁵ and R ⁴⁶ are bonded, such as pyrrolidine ring, morpholine ring, oxidine ring and other nitrogen-containing non-ferrous ring. The aromatic 4- to 7-membered ring preferably includes a 4- to 7-membered ring having only one nitrogen atom as a heteroatom, such as a pyrrolidine ring and a pyridine ring.

As R ⁵⁸ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable.

As R ⁴¹ to R ⁴⁴ , R ⁵⁶ , and R ⁵⁸ to R ⁶⁰ , preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, more preferably each independently a saturated hydrocarbon group having 1 to 8 carbon atoms The hydrocarbon group is either a group represented by the following formula. R ⁵⁶ , R ⁵⁸ to R ⁶⁰ are further preferably a group represented by the following formula. In the following formula, * represents a bond terminal with a nitrogen atom.

R ⁴⁵ to R ⁴⁶ are preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or a group in which -CH ₂ - in an alkyl group having 2 to 20 carbon atoms is replaced by at least one of -O- and -CO- group, or an aromatic hydrocarbon group which may have a substituent; or, R ⁴⁵ and R ⁴⁶ are bonded together to form a ring together with the nitrogen atom to which the R ⁴⁵ and R ⁴⁶ are bonded. In some embodiments, R ⁴⁵ to R ⁴⁶ may each independently be a saturated hydrocarbon group with a carbon number of 1 to 8, an alkoxyalkyl group, or a group as shown in the above figure, or R ⁴⁵ and R ⁴⁶ are bonded to A 4- to 7-membered ring is formed with only 1 nitrogen atom as a heteroatom. In the following formula, * represents a bond terminal with a nitrogen atom.

In addition, the alkyl group having 1 to 8 carbon atoms in R ⁴⁷ to R ⁵⁴ can be exemplified by the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group in the aforementioned R ⁴¹ , and the carbon number is 1 to 8. 8 saturated hydrocarbon groups. In addition, an alkyl group having 2 to 8 carbon atoms in R ⁴⁷ to R ⁵⁴ , wherein -CH ₂ - is replaced by at least one of -O- and -CO-. Among them, the adjacent -CH ₂ - will not be substituted with -O- at the same time, and the terminal -CH ₂ - will not be substituted with ^-O- or ^-CO- ). The alkyl group having 2 to 20 carbon atoms, in which -CH ₂ - is replaced by at least one of -O- and -CO-. A group having 8 or less carbon atoms.

R ⁴⁷ to R ⁵⁴ are preferably each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

R ⁴⁷ to R ⁵⁴ may each independently be a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom. R ⁶¹ is preferably a hydrogen atom.

The r-valent metal ions represented by M ^r+ include alkali metal ions such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as beryllium ions, magnesium ions, calcium ions, strontium ions, and barium ions; titanium ions, Zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion and other transition metal ions; zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion and other typical metal ions, etc. . r is 1 or more, preferably 2 or more, preferably 5 or less, or 4 or less, and more preferably 3 or less. Moreover, quaternary ammonium ions, such as a tetraalkylammonium ion, are mentioned as a substituted or unsubstituted ammonium ion represented by M ^r+ .

M ^r+ may be a hydrogen ion or an r-valent metal ion, more preferably an alkaline earth metal ion, a typical metal ion, etc., more preferably an alkaline earth metal ion and a zinc ion, and still more preferably an alkaline earth metal ion.

In formula (I), the number of ^Mr+ is R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ , the number of -SO ₃ ^- on the ring T ¹ , and the number of -SO ₂ -N ^- -SO ₂ - The sum (k) of the number of R ^f is less than the number of 1. Therefore, the valence of compound (I) is 0, that is, it is an electrically neutral compound.

The fluoroalkyl group having 1 to 12 carbon atoms in R ^f includes monofluoromethyl, difluoromethyl, perfluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, and tetrafluoroethyl base, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluorobutyl base, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, perfluorobutyl and the like. Among them, as the fluoroalkyl group represented by R ^f , a perfluoroalkyl group is preferable. In addition, the carbon number of the fluoroalkyl group represented by R ^f is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3.

In formula (I), R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . The sum (k) of the numbers of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^f possessed by R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ is 1 or more, preferably 1 to 7, more preferably 2 to 7, or 2 to 4, even more preferably 2 or 3.

-SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f preferably satisfies at least one or more conditions selected from the following (a) to (d), and more preferably satisfies the conditions selected from (a) and (b) ) at least one or more of the conditions. (a) contains as any one of the above-mentioned R ⁴⁷ to R ⁵⁴ ; (b) is bonded to any one of the aromatic hydrocarbon groups represented by R ⁴¹ to R ⁴⁴ which may have a substituent with 6 to 20 carbon atoms; ( c) bonding to any one of aralkyl groups having 7 to 30 carbon atoms which may have a substituent represented by R ⁴¹ to R ⁴⁴ ; and (d) a hydrogen atom of an aromatic heterocyclic ring represented by T ¹ Any one of the substituted aromatic hydrocarbon groups having 6 to 20 carbon atoms is bonded.

However, when -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is bonded to an aromatic hydrocarbon group or an aralkyl group, it is preferably -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is directly bonded to an aromatic hydrocarbon group or an aromatic hydrocarbon ring which is an aralkyl group. That is, it is preferable that -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is substituted with a hydrogen atom bonded to an aromatic hydrocarbon ring.

In some embodiments, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f at R ⁴¹ to R ⁴⁴ is an aromatic hydrocarbon group with 6 to 20 carbon atoms or R ⁴¹ to R that may have substituents ⁴⁴ is an aromatic hydrocarbon ring (eg, a benzene ring) in an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and is bonded to the para position with respect to the bonding position to the nitrogen atom.

When compound (I) contains plural -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , plural -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f may be bonded to the same aromatic hydrocarbon ring, but is preferably bonded to a different aromatic hydrocarbon ring.

Compound (I) preferably does not have an ethylenically unsaturated bond.

In some embodiments, compound (I) can be a compound represented by the following formulas (A1-1) and (A1-2):

Compound (I) can be produced, for example, by sulfonating a compound represented by formula (IC) (hereinafter sometimes referred to as compound (IC)). Compound (IC) is preferably hydrochloride, phosphate, perchlorate, BF ₄ salt or PF ₆ salt or the like.

In formula (IC), R ¹ to R ⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted carbon number The aralkyl group of 7 to 30, in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amine group or a halogen atom, and in the saturated hydrocarbon group The contained -CH ₂ - may be replaced by at least one of -O- and -CO-. R ¹ and R ² may bond and form a ring together with the nitrogen atom to which the R ¹ and R ² are bonded, and R ³ and R ⁴ may bond and form a ring together with the nitrogen atom to which the R ³ and R ⁴ are bonded. R ⁷ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and -CH ₂ - constituting the alkyl group may be replaced by -O- and -CO- at least one of the. R ⁸ and R ¹² can be bonded to each other to form -NH-, -S- or -SO ₂ -. Ring T ¹⁰ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, which may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have a substituent. M ¹ represents Cl ⁻ , phosphate ion, perchlorate ion, BF ₄ ⁻ or PF ₆ ⁻ .

式(IB)中，R^f 與前述之R^f 同義。When compound (I) is a compound having -SO ₃ ^- group and not having -SO ₂ -N ^- -SO ₂ -R ^f (hereinafter sometimes referred to as "compound (A1-a)"), Compound (A1-a) can be reacted with a compound represented by formula (IB).

In formula (IB), R ^f is synonymous with the aforementioned R ^f .

In addition, when compound (I) is a compound in which M ^r+ is a hydrogen ion in formula (I) (hereinafter sometimes referred to as compound (IA-2)), compound (IA-2) can be combined with a compound containing an r-valence. Metal ions react with halides (preferably chlorides), acetates, phosphates, sulfates, silicates or cyanides.

As the sulfonation method, any appropriate method can be used, for example, the method described in Journal of Organic Chemistry, (1994), Vol. 59, No. 11, pp. 3232-3236.

In some embodiments, the colorant (A) may further include a second colorant in addition to the first colorant.

式(II)In some embodiments, the second colorant is a compound having the structure of formula (II):

Formula (II)

In formula (II), R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or -R ²⁰ -Si( R ¹⁹ ) ₃ . The three R ¹⁹ in the aforementioned -R ²⁰ -Si(R ¹⁹ ) ₃ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R ²⁰ is carbon The alkylene group of numbers 1 to 10, the -CH ₂ - in the alkylene group constituting R ²⁰ can be replaced by -O-, -CO-, -NR ²¹ -, -OCO-, -COO-, -OCONH-, -CONH-, or -NHCO- substitution. The hydrogen atom of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms can be replaced by a halogen atom, and -CH ₂ - can be replaced by -O-, -CO-, -NR ²¹ -, -OCO-, -COO- , -OCONH-, -CONH-, or -NHCO- substituted, but in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, the adjacent -CH ₂ - will not be substituted at the same time, and the terminal -CH ₂ - will not be substituted at the same time. will be replaced. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms. R ¹⁷ and R ¹⁸ are each independently -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ -Z ⁺ , -CO ₂ ^- , -CO ₂ H, -CO ₂ -Z+, -CO ₂ R ²⁴ , -SO ₃ R ²⁵ , or -SO ₂ NR ²² R ²³ , wherein R ²⁴ and R ²⁵ are each independently a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the Hydrogen atoms can be replaced by halogen atoms. Z ⁺ may be [N(R ²⁶ ) ₄ ] ⁺ , Na ⁺ , or K ⁺ ; the four R ²⁶ are each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms; q is an integer of 0 to 4; a is 0 or 1.

In some embodiments, when formula (II) has -SO ₃ ^- , its number is one.

The substituents described in the optionally substituted phenyl group among R ¹¹ to R ¹⁴ include a halogen atom, an alkyl group, -R ²⁴ , -OH, -OR ²⁴ , -SO ₃ ^- , -SO ₃ H , -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ²⁴ , -SR ²⁴ , -SO ₂ R ²⁴ , -SO ₃ R ²⁴ or -SO ₂ NR ²⁴ R ²⁵ . Among these, as the substituents, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ²⁴ R ²⁵ are preferable. As -SO ₃ ^- Z ⁺ in this case, -SO ₃ ^-+ N(R ²¹ ) ₄ is preferable.

A monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ¹¹ to R ¹⁴ and R ²⁰ , for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl Alkyl, decyl, and other straight-chain alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl and other branched chain alkyl groups; cyclopropyl, cyclopentyl, cyclohexyl , cycloheptyl, cyclooctyl and other alicyclic saturated hydrocarbon groups with 3 to 10 carbon atoms.

Examples of R ²⁰ in the aforementioned -R ²⁰ -Si(R ¹⁹ ) ₃ include alkylene groups such as methylidene, ethylidene, and propylidene. Examples of the alkyl group having 1 to 4 carbon atoms in R ¹⁹ include methyl, ethyl, propyl, and butyl. As the alkoxy group having 1 to 4 carbon atoms in R ¹⁹ , for example, a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group and the like can be mentioned.

-OR ²⁴ can be exemplified by methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy Base et al.

For -CO ₂ R ²⁴ , methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, eicosyloxycarbonyl and the like can be exemplified.

-SO ₃ R ²⁵ can be exemplified by methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosyloxy Sulfonyl etc.

-SO ₂ NR ²² R ²³ includes sulfamoyl; base, N-butylaminosulfonyl, N-isobutylaminosulfonyl, N-2-butylaminosulfonyl, N-tert-butylaminosulfonyl, N-amylaminosulfonyl base, N-(1-ethylpropyl) sulfamoyl, N-(1,1-dimethylpropyl) sulfamoyl, N-(1,2-dimethylpropyl) sulfamoyl Acyl, N-(2,2-dimethylpropyl) sulfamoyl, N-(1-methylbutyl) sulfamoyl, N-(2-methylbutyl) sulfamoyl , N-(3-methylbutyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) sulfamoyl N,N-2 substituted sulfasulfonyl and the like.

In some embodiments, formula (II) is electrically neutral, that is, a is zero. In some embodiments, the formula (II) has a monovalent positive charge, and in this case, the formula (II) can be paired with a common monovalent anion, such as a halide ion.

In some embodiments, formula (II) may have the structures shown in (A2-1) to (A2-10) below:

As the second colorant, commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemical Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) can be used as starting materials, refer to The synthesis was performed in Japanese Patent Laid-Open No. 2010-32999.

In some embodiments, when the second colorant used also contains silicon (eg, in formula (II), at least one of R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ is -R ²⁰ -Si(R ¹⁹ ) ₃ ), compared with other types of second colorants, it can also contain silyl monomer units of silicon (the structure of which will be described later), and has better compatibility.

In some embodiments, in addition to the first colorant or the first colorant/second colorant, the colorant resin composition may have other colorants other than the first colorant and the second colorant according to actual needs , such as dyes or pigments other than the first and second colorants.

The dyes other than the first colorant and the second colorant are not particularly limited, and well-known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dyes include compounds classified as substances having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Shiyesha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, square dyes Acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes, etc. The pigment is not particularly limited, either, and known pigments can be used, and examples thereof include pigments classified as pigments in a color index (published by The Society of Dyers and Colourists). In some embodiments, the colorant in the colored resin composition (eg, when there is only the first colorant in the colored resin composition, is calculated as the first colorant; when there is the first colorant, and the non-first colorant If the solid component is 100 parts by weight, it is preferably 1 to 40 parts by weight, more preferably 3 to 35 parts by weight. When the content of the colorant is within the above-mentioned range, the color density when used as a color filter is sufficient, and the composition can contain necessary amounts of the resin and the polymerizable compound, so that a pattern with sufficient mechanical strength can be formed. The "solid component" in this case refers to the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid component and the content of each component relative thereto can be measured by an appropriate analytical method such as liquid chromatography or gas chromatography, for example.

In some embodiments, the weight of the first colorant is 1 to 40 times the weight of the second colorant, preferably 3 to 30 times.

According to actual needs, the solid component may contain a dispersant, so that the colorant can be uniformly dispersed in the solution. As said dispersing agent, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. surfactants are mentioned, for example. These dispersants may be used alone or in combination of two or more. The pigment dispersant is represented by a trade name, and examples include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOREN (manufactured by Kyōeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (manufactured by CIBA Corporation) , Adisper (manufactured by Ajinomoto fine-techno Co., Ltd.), Disperbyk (manufactured by BYK Chemicals), and the like.

In some embodiments, the resin (B) may comprise an alkali-soluble resin such as, but not limited to, a (meth)acrylic acid derived structural unit.

In some embodiments, the number of epoxydicyclopentenyl monomer units in resin (B) accounts for 8% to 50% of the total number of all monomer units in resin (B), preferably 10 to 45% by weight, More preferably, it is 12 to 42 wt %.

According to some embodiments of the present disclosure, when the content of the epoxydicyclopentenyl monomer unit is lower than the above-mentioned lower limit, the effect of strengthening the cross-linked polymer network of the resin may be reduced, and when When the content of epoxydicyclopentenyl monomer units is higher than the above-mentioned upper limit, there may be a crowding effect on the content of other necessary components, and thus the crosslinking strength of the polymer network may be reduced. Therefore, according to some embodiments of the present disclosure, when the content of the epoxydicyclopentenyl monomer unit is within the above range, the best effect can be provided for improving the heat resistance and stability of the overall structure.

In some embodiments, the ratio of the number of epoxy dicyclopentenyl monomer units to the number of silyl monomer units in resin (B) is 1:0.02-1:0.08, preferably 1:0.03-1 : 0.07, more preferably 1:0.035 to 1:0.06.

According to some embodiments of the present disclosure, when the ratio of the number of epoxydicyclopentenyl monomer units to the number of silane-based monomer units is within the above range, the silicon atoms or silane functional groups of the silane-based monomer units It will not be too much to adversely affect the predetermined chemical and physical properties of the colored resin composition, and can achieve the effect of maintaining the predetermined characteristics of the colored resin composition and at the same time assisting in enhancing the crosslinking strength of the polymer network.

In some embodiments, relative to 100 parts by weight of epoxydicyclopentenyl monomer units, the silane-based monomer unit is 2 to 8 parts by weight, preferably 3 to 7 parts by weight, more preferably 3.5 parts by weight to 6 parts by weight.

其中，R1表示氫原子或者是碳數1至4的烷基，所述烷基中所含的氫原子可被羥基取代，X1表示單鍵、-R3-、-R3-O-、-R3-S-、或-R3-NH-，其中R3表示碳數1至6的伸烷基，n為正整數； [化學式2]

其中，R2表示氫原子或者是碳數1至4的烷基，所述烷基中所含的氫原子可被羥基取代，X2表示單鍵、-R3-、-R3-O-、-R3-S-、或-R3-NH-，m為正整數。In some embodiments, the epoxydicyclopentenyl monomer unit of resin (B-1) may include a first monomer unit having a structure as shown in Chemical Formula 1, and a second monomer unit having a structure as shown in Chemical Formula 2. At least one of the two monomer units: [Chemical formula 1]

Wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group, and X1 represents a single bond, -R3-, -R3-O-, -R3- S-, or -R3-NH-, wherein R3 represents an alkylene group having 1 to 6 carbon atoms, and n is a positive integer; [Chemical formula 2]

Wherein, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group, and X2 represents a single bond, -R3-, -R3-O-, -R3- S-, or -R3-NH-, m is a positive integer.

[化學式2A]

In some embodiments, the epoxydicyclopentenyl monomer unit of resin (B-1) may include a monomer unit having a structure as shown in Chemical Formula 1A and a monomer unit having a structure as shown in Chemical Formula 2A: [Chemical formula 1A]

[Chemical formula 2A]

In some embodiments, the resin (B-1) may be a polymer containing a constituent unit derived from at least one monomer of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

In some embodiments, the resin (B-1) may have a structural unit derived from a monomer (m2-1), and a monomer ( Hereinafter referred to as "monomer (m2-2)") is a copolymer of constituent units derived. The above-mentioned copolymer may contain other constituent units. As the other structural unit, for example, a structural unit derived from a monomer (hereinafter referred to as "monomer (m2-3)") different from the monomer (m2-1) and the monomer (m2-2), or having an alkene It is a structural unit of unsaturated bonds, etc. In the copolymer, each of the above-mentioned structural units contains only one type, but may contain two or more types.

Examples of the monomer (m2-1) include (1) unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid; (2) maleic acid, Fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1 ,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; (3) methyl-5-nor Bornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5- Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2- 2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; (4) maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; (5) succinic acid mono[2-(methyl) Unsaturated mono[(meth)acryloyloxy groups of polyvalent carboxylic acids of divalent or higher such as acryloyloxyethyl]ester, mono[2-(meth)acryloyloxyethyl]phthalate, etc. Alkyl]esters; or (6) unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as (6) α-(hydroxymeth)acrylic acid, and the like.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the viewpoint of the copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

The monomer (m2-2) refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (eg, an oxirane ring, an oxetane ring, or a tetrahydrofuran ring) and an ethylenically unsaturated bond. The monomer (m2-2) may preferably be a monomer having a cyclic ether having a carbon number of 2 to 4 and a (meth)acryloyloxy group.

Examples of the monomer (m2-2) include a monomer (m2-2-1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-1)" "), a monomer (m2-2-2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-2)"), or A monomer (m2-2-3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-3)") and the like.

Examples of the monomer (m2-2-1) include monomers (m2-2-1a) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "" Monomer (m2-2-1a)"), monomer (m2-2-1b) having a structure in which alicyclic unsaturated hydrocarbons are epoxidized (hereinafter sometimes referred to as "monomer (m2-2-1b)" ”).

As the monomer (m2-2-1a), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Examples of the monomer (m2-2-1a) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, and glycidyl ethylene base ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2, 3,4-Tris(glycidoxymethyl)styrene, 2,3,5-Tris(glycidoxymethyl)styrene, 2,3,6-Tris(glycidoxymethyl)benzene Ethylene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

Examples of the monomer (m2-2-1b) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Co., Ltd.), 3,4-Epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMERA400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMERA400; Co., Ltd.) Co., Ltd. Daicel), the compound represented by the following formula (III), the compound represented by the formula (IV), and the like.

In formula (III) and formula (V), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group. X ^a and X ^b represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-. R ^c represents an alkylene group having 1 to 6 carbon atoms. * indicates the bonding end with O.

As the compound represented by the formula (III), the compound represented by any one of the formula (III-1) to the formula (III-15), and the like can be exemplified. Among them, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III) are preferred The compound represented by -15).

As the compound represented by the formula (IV), the compound represented by any one of the formula (IV-1) to the formula (IV-15), and the like can be exemplified. Among them, formula (IV-1), formula (IV-3), formula (IV-5), formula (IV-7), formula (IV-9) or formula (IV-11) to formula (IV) are preferred. The compound represented by -15) is more preferably a compound represented by formula (IV-1), formula (IV-7), formula (IV-9) or formula (IV-15).

The compound represented by the formula (III) and the compound represented by the formula (IV) may each be used alone, or two or more of them may be used in combination. When the compound represented by the formula (III) and the compound represented by the formula (IV) are used in combination, their content ratio [the compound represented by the formula (III): the compound represented by the formula (IV)] is on a molar basis , preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

Examples of the monomer (m2-3) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, (meth)acrylate ) 3-butyl acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate ) cyclopentyl acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (In this technical field, it is called "dicyclopentyl (meth)acrylate" as a common name. In addition, it may be called "tricyclodecyl (meth)acrylate"), (meth)acrylate tricyclo [5.2.1.0 ^2,6 ] Decen-8-yl ester (in the technical field, as a common name, referred to as "(meth)acrylic acid dicyclopentenyl ester"), (meth)acrylic acid dicyclopentyloxyethyl Esters, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylate (meth)acrylates such as naphthyl acrylate and benzyl (meth)acrylate; (meth)acrylic acid containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate Esters; Diethyl maleate, diethyl fumarate, diethyl itaconic acid and other dicarboxylic acid diesters; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2. 1] Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1] Hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2- alkene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6 -diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1 ]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-3-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl) Bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide Amine, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-methylene Dicarbonyl imine derivatives such as lyimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl) maleimide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride , acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide are preferred. Imide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and benzyl(meth)acrylate, etc.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. The resin (B-1) having such a structural unit can be obtained by making a polymer containing a structural unit derived from the monomer (m2-1) and a structural unit derived from the monomer (m2-2), and It is obtained by reacting a monomer having a reactive group with the aforementioned constituent unit and an ethylenically unsaturated bond.

As a constitutional unit having an ethylenically unsaturated bond, for example, a constitutional unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, or by adding 2 to a maleic anhydride unit can be used. - A structural unit obtained by hydroxyethyl (meth)acrylate, a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, and in a structural unit having a hydroxyl group A structural unit obtained by adding a carboxylic acid anhydride, etc.

The polymer containing the structural unit derived from the monomer (m2-1) can be produced by, for example, polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent, etc. are not particularly limited, and those generally used in this field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic Oxides (benzyl peroxide, etc.) may be used as a solvent if each monomer of the resin (B-1) is dissolved, and examples thereof include the solvent used for the colored resin composition of the present invention, as described later.

In the production of a polymer containing a constituent unit derived from the monomer (m2-1), as the monomer, a carboxylic acid anhydride having an ethylenically unsaturated bond can be used. As the carboxylic acid anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydro Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]heptyl-2- Olefins, etc.

As the resin (B-1), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decane acrylate may be mentioned, for example. Resins such as ester/(meth)acrylic acid copolymer; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/( Meth)acrylic acid copolymer, 3,4-epoxytricyclo[ ^5.2.1.02.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (Meth)acrylooxymethyl oxetane/(meth)acrylic acid/styrene copolymer, benzyl(meth)acrylate/(meth)acrylic acid copolymer styrene/(meth) Acrylic copolymers and resins and the like described in Japanese Patent Laid-Open No. 9-106071, Japanese Patent Laid-Open No. 2004-29518, and Japanese Patent Laid-Open No. 2004-361455.

The weight average molecular weight (Mw) of the resin (B-1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000. The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the resin (B-1) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value (solid content conversion value) of the resin (B-1) is preferably 10 to 300 mg-KOH/g, or may be 20 to 250 mg-KOH/g, or may be 20 to 200 mg-KOH/g, or may be 20 to 170 mg-KOH/g, or 30 to 170 mg-KOH/g. Here, the acid value is a measured value of the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B-1), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

In some embodiments, when the resin (B-1) and the resin (B-2) described later are used at the same time, the weight ratio of the resin (B-1) to the solid component is smaller than the weight ratio of the resin (B-2) to the solid component The weight ratio of the part. In this way, the colored resin composition can still maintain better resolution under high exposure dose. In some embodiments, the total weight of resin (B-1) is 50% or less of the total weight of resin (B-2), or may be 45% or less.

In some embodiments, when the resin (B-1) and the resin (B-2) described later are used at the same time, when the solid component is 100 parts by weight, the resin (B-1) and the resin (B-2) described later are ) is 20 to 60 parts by weight in total, or may be 30 to 55 parts by weight.

其中，R4 表示氫原子或甲基； R5～R7各自獨立表示氫原子、碳數1～6之烷基或碳數1～6之烷氧基，但R5～R7之中至少1個是碳數1～6之烷氧基； p為正整數，q為1～10之整數。In some embodiments, the silyl monomer unit of the resin (B-2) may have a structure as shown in Chemical Formula 3: [Chemical Formula 3]

Wherein, R4 represents a hydrogen atom or a methyl group; R5 to R7 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, but at least one of R5 to R7 is a carbon number. 1-6 alkoxy groups; p is a positive integer, q is an integer of 1-10.

By using a silicone resin having a silane-based monomer unit as shown in Chemical Formula 3 in combination with the first colorant, the formed colored resin composition film layer can still be formed with good resolution under high exposure. Micro hole pattern.

Examples of the alkyl group having 1 to 6 carbon atoms in R5 to R7 include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, isopentyl, and neopentyl. .

Examples of alkoxy groups having 1 to 6 carbon atoms in R5 to R7 include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, isopropoxy, isobutoxy The oxy group includes isopentyloxy and neopentyloxy.

R5 to R7 may each independently be methoxy, ethoxy or propoxy, more preferably methoxy or ethoxy. q is an integer that may be 1 to 6, or an integer that may be 1 to 3.

In some embodiments, the silane-based monomer unit may have the structure shown in Chemical Formula 3A: [Chemical Formula 3A]

In some embodiments, the silane-based monomer unit may have the structure shown in Chemical Formula 3B: [Chemical Formula 3B]

In some embodiments, the resin (B-2) comprising a silane-based monomer unit may further comprise a constituent unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter referred to as "the constituent unit (b1-2)". 2)"), and a copolymer of other constituent units (b1-3) (hereinafter referred to as "constituent units (b1-3)"). In this case, the other constitutional unit (b1-3) represents a constitutional unit different from the silyl monomer unit and the constitutional unit (b1-2). In (B-2), each of the silyl group monomer unit, the structural unit (b1-2) and the structural unit (b1-3) may contain only one kind of each, or two or more kinds of each may be contained.

Examples of the acidic group contained in the constituent unit (b1-2) include a carboxyl group, a phosphoric acid group (-OP(=O)(OH) ₂ ), and a sulfo group (-S(=O) ₂ OH), and among them, preferred are carboxyl.

From the viewpoint of solvent resistance, when the total of the total constituent units in the copolymer is 100 mol %, the content of the silyl monomer unit may be 1 to 50 mol %, more preferably 5 to 40 mol % mol%, or 10~30 mol%.

When the total of the total structural units in the copolymer is 100 mol %, the content of the structural unit (b1-2) may be 10 to 50 mol %, more preferably 15 mol %, from the viewpoint of developability. ~45 mol%, or 20~40 mol%.

In order to make the formed colored resin composition have better developability, the weight average molecular weight (Mw) of (B-2) can be 1,000-50,000, or 2,000-40,000. The above-mentioned weight average molecular weight (Mw) can be obtained by converting from the value of polystyrene by Gel Permeation Chromatography (GPC).

In some embodiments, the silane group equivalent in the resin (B-2) is preferably 400-4,000, more preferably 500-3,000, from the viewpoints of thermal decomposition resistance, thermal yellowing resistance and solvent resistance. When the silane group equivalent of the resin (B-2) is 400 or more, the thermal decomposition resistance and thermal yellowing resistance of the colored pattern or colored coating film can be improved. The silane group equivalent of resin (B-2) is based on the following formula: Silane group equivalent = weight average molecular weight of resin (B-2) / average number of silane groups in one molecule of resin (B-2) , the calculated value. The silane group equivalent can be calculated from the amount of monomers added in the production of the resin (B-2).

In some embodiments, when the resin (B-2) is a copolymer containing the constituent unit (b1-2), the acid value of the resin (B-2) may be 20-300 mg KOH/g from the viewpoint of developability , more preferably 30-200mg KOH/g. The acid value of the resin (B-2) is a value measured according to JISK69015.3 using a mixed indicator of bromothymol blue and phenol red, which is measured by neutralizing 1 g of the resin (B-2) , the value obtained by the required amount (mg) of potassium hydroxide can be obtained, for example, by titration with an aqueous potassium hydroxide solution.

In some embodiments, after alkaline development, in order to form a good pattern without defects and peeling, the polymerizable compound (that is, the photopolymerizable monomer (C) in the resin (B-2) and the colored resin composition will be used in the subsequent further details), there may be specific ratios. In some embodiments, if the polymerizable compound is 100 parts by weight, the content of the resin (B-2) may be 5 to 400 parts by weight, 7.5 to 375 parts by weight, or 10 to 350 parts by weight.

[式(2b)中符號的意義如上所述]In some embodiments, the resin (B-2) can be a compound (m1-1) represented by the formula (2b), or a single compound formed by the compound (m1-1) and other compounds in the presence of a polymerization solvent. It is obtained by copolymerization by free radical polymerization or other suitable methods.

[The meanings of the symbols in the formula (2b) are as described above]

In some embodiments, the resin (B-2) can be prepared by dissolving the compound (m1-1) and other compounds according to actual needs in a solvent for polymerization to form a solution, and then adding a polymerization initiator to the solution. Obtained by reacting at 50~130°C for 1-20 hours.

In some embodiments, the resin (B-2) containing the silane-based monomer unit, the structural unit (b1-2) and the structural unit (b1-3) can be prepared by compounding the compound (m1-1) in the presence of a solvent for polymerization. ), polymerizable unsaturated compounds (m1-2) having acidic groups (hereinafter referred to as "compounds (m1-2)"), and other polymerizable unsaturated compounds (m1-3) (hereinafter referred to as "compounds (m1-3)" The monomer mixture composed of m1-3)") is obtained by copolymerization by known free-radical polymerization methods. Here, the other polymerizable unsaturated compound (m1-3) refers to a polymerizable unsaturated compound different from the compound (m1-1) and the compound (m1-2). In addition, the silyl monomer unit is derived from the compound (m1-1), the structural unit (b1-2) is derived from the compound (m1-2), and the structural unit (b1-3) is derived from the compound (m1-3) .

In some embodiments, the resin (B-2) can be prepared by dissolving the compound (m1-1), the compound (m1-2), and the compound (m1-3) in a solvent for polymerization to form a solution, then in the A polymerization initiator is added to the solution, and it is obtained by reacting at 50-130° C. for 1-20 hours.

As the compound (m1-1), for example, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, , 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxy propylpropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, etc. Among them, 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acrylooxypropyltriethoxysilane are from the viewpoints of availability and reactivity. better. In this case, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid. Other similar recording methods have the same meaning as this.

The acidic group possessed by the compound (m1-2) may be, for example, a carboxyl group, a phosphoric acid group (-OP(=O)(OH) ₂ ), or a sulfo group (-S(=O) ₂ OH), among which a carboxyl group is preferred.

Specific examples of the compound (m1-2) are, for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acrylooxyethylsuccinic acid, 2-acryloyloxy Ethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. Among these, (meth)acrylic acid is preferable from the viewpoint of easiness of acquisition and reactivity.

Examples of the compound (m1-3) include (1) dienes such as butadiene; (2) methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid Amyl, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Benzyl meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate Cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-Methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, allyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid 1,1,1-Trifluoroethyl, perfluoroethyl (meth)acrylate, perfluoron-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenyl (meth)acrylate methyl ester, cumyl (meth)acrylate (cumyl), 3-(N,N-dimethylamino)propyl (meth)acrylate, glycerol mono(meth)acrylate, butanetriol mono (Meth)acrylate, Pentatriol mono(meth)acrylate, Dicyclopentenyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, (meth)acrylate Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, (meth)acrylate 2 -Isocyanatoethyl, (meth)acrylic acid 2-isocyanatopropyl, (meth)acrylic acid 3-isocyanatopropyl, (meth)acrylic acid 2-isocyanato-1- Methyl ethyl ester, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, the aforementioned isocyanate groups Isocyanato groups of ethylenically unsaturated compounds, compounds with blocked isocyanato groups that have been blocked using a blocking agent, N,N-dimethylaminoethyl (meth)acrylate, (methyl) ) N,N-diethylaminoethyl acrylate, N-tert-butylaminoethyl (meth)acrylate, tetramethylpiperidine (meth)acrylate, hexamethylpiperidyl (methyl) (meth)acrylates such as acrylates; (3) (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethyl N,N-dipropylamide (meth)acrylate, N,N-diisopropylamide (meth)acrylate, anthrylamide (meth)acrylate (meth)acrylic acid amides such as amine, N-isopropyl (meth) acrylamide, (meth)acrylic acid morpholine, diacetone (meth) acrylamide, etc.; (4) norbornene ( bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4 .0.12,5.17,10]hept-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]hept-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]heptane -3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]dec-8-ene, tricyclo[5.2.1.02,6]dec-3-ene, tricyclo[4.4.0.12,5]deca Mono-3-ene, tricyclo[6.2.1.01,8]undec-9-ene, tricyclo[6.2.1.01,8]undec-4-ene, tetracyclo[4.4.0.12,5.17,10.01,6 ]hept-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]hept-3-ene, 8-ethylenetetracyclo[4.4.0.12,5.17,12]hept-3- ene, 8-ethylenetetracyclo[4.4.0.12,5.17,10.01,6]hept-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadec-4-ene, pentacyclo[ 7.4.0.12, 5.19, 12.08, 13] Pentadec-3-ene, 5-norbornene-2,3-dicarboxylic anhydride, (meth)acrylic acid-aniline, (meth)acrylonitrile, propylene Vinyl compounds of aldehyde, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl pyridine, vinyl acetate, vinyl toluene, etc.; (5) styrene, α-, o-, styrene, etc. m-, p-alkyl, nitro, cyano, amide derivatives; (6) diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. (7) Unsaturated polybasic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc.

Among these, from the viewpoint of availability and reactivity, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and (meth)acrylic acid Dicyclopentyl ester, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, N,N-diethylamino (meth)acrylate Ethyl ester, N,N-dimethylamide (meth)acrylate, morpholine (meth)acrylate, styrene, vinyltoluene and norbornene are preferred, methyl (meth)acrylate, (methyl) ) benzyl acrylate, dicyclopentyl (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, styrene and Vinyltoluene is preferred. The compound (m1-3) may be used alone or in two or more. Among them, from the viewpoint of thermal decomposition resistance and thermal yellow discoloration, alkyl (meth)acrylate is preferred, methyl (meth)acrylate, benzyl (meth)acrylate, and dicyclopentyl (methyl) Acrylates are preferred.

Also, from the viewpoint of improving solvent resistance, a polymerizable compound having a functional group reactive with an acid group is preferable, and specifically, a glycidyl group, an oxetanyl group, an isocyanate group, Or a polymerizable compound with a blocked isocyanate. From the viewpoints of easiness of acquisition and reactivity, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methylmethacrylate, etc. are preferably mentioned.

The blocking agent used as the block of the above-mentioned isocyanate group can be exemplified by ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam and other lactamides; Methanol, Ethanol, Propanol, Butanol, Ethylene Glycol, Methyl Salusol, Butyl Salusol, Methyl Carbitol, Benzyl Alcohol, Phenyl Salusol, Sugar Alcohol, Cyclohexanol, etc. Phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol and other butylphenol, p-tert-octylphenol, nonylphenol, dinonyl Phenols such as phenol, styrene phenol, hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol, etc.; dimethyl malonate, diethyl malonate, ethyl malonate Activated methane series such as methyl acetoacetate, ethyl acetate, acetone acetone, etc.; mercaptan series such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.; diphenylamine, benzene Amines such as naphthylamine, aniline, carbazole, etc.; acid amides such as acetonitrile, acetonitrile, acetamide, benzylamine, etc.; succinic acid imide, maleic acid amide Acid imide series such as imine; imidazole series such as imidazole, 2-methyl imidazole, 2-ethyl imidazole; urea series such as urea, thiourea, vinyl urea, etc.; phenyl N-phenylcarbamate, Carbamates such as 2-oxazolidinone; imines such as ethyleneimine, polyethyleneimine, etc.; formaldehyde oxime, acetaldoxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl Ketoxime series such as ketoxime, cyclohexanone oxime, etc.; bisulfite series such as sodium bisulfite, potassium bisulfite, etc.

In order to control the weight molecular weight and molecular weight distribution (Mw/Mn) of the resin (B-2) within a specific range, and at the same time obtain a coloring pattern with the desired solvent resistance, the polymerization solvent used in the copolymerization reaction, Preferably, it is a C3-C10 hydroxyl-containing solvent. Specific examples of the hydroxyl-containing solvent having 3 to 10 carbon atoms include monoalcohols such as propanol, butanol, pentanol, hexanol, octanol, nonanol, tridecanol, dodecanol, and benzyl alcohol. , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether (Poly)polyolefin glycol monoalkyl ethers such as propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-dibutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. These C3-C10 hydroxyl-containing solvent systems can be used individually by 1 type or in combination of 2 or more types.

The polymerization solvent used in the copolymerization reaction may contain other solvents other than the aforementioned polymerization solvent. Examples of other solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like (polyethylene glycol monoethyl ether acetate). ) polyolefin glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ether Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate Ester, Ethyl 2-Hydroxy-2-Methylpropionate, Methyl 3-Methoxypropionate, Ethyl 3-Methoxypropionate, Methyl 3-Ethoxypropionate, 3-Ethoxypropionate Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl -3-Methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate , n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate Esters, ethyl acetate, 2-oxobutyrate, etc.; Aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylformamide, etc. Carboxylic acid amides such as N-dimethylacetamide and the like. Among these, from the viewpoint of reactivity, (poly)polyolefin glycol monoalkyl ether acetate-based solvents such as propylene glycol monomethyl ether acetate are preferable.

For the polymerization solvent used in the copolymerization reaction, the content ratio of the hydroxyl group-containing solvent having 3 to 10 carbon atoms is preferably 10% by weight to 100% by weight, preferably 20% by weight to 100% by weight.

The amount of the polymerization solvent used in the copolymerization reaction is not particularly limited. Preferably, when the total amount of compound (m1-1), compound (m1-2) and compound (m1-3) added is 100 parts by weight, it is preferably 30 parts by weight to 1000 parts by weight, or 50 parts by weight ~800 parts by weight.

The polymerization initiator that can be used in this copolymerization reaction is not particularly limited, and examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylene) valeronitrile), 2,2'-azobis(isobutyric acid) dimethyl ester, benzyl peroxide, tert-butylperoxy-2-ethylhexanoate, etc. These polymerization initiators may be used alone or in combination of two or more. The usage amount of the polymerization initiator is not particularly limited, but when the total amount of the compound (m1-1), the compound (m1-2) and the compound (m1-3) added is 100 parts by weight, it is preferably 0.5 Parts by weight to 20 parts by weight, more preferably 1.0 parts by weight to 10 parts by weight.

In some embodiments, if the solid component is 100 parts by weight, the resin (B-2) may be 20 to 60 parts by weight, preferably 30 to 55 parts by weight. When the content of the resin (B-2) is within this range, the film formed by the colored resin composition can obtain better hole pattern resolution.

In some embodiments, the resin (B) may further comprise at least one structural unit having an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and/or having a (meth)acrylate and/or a (meth)acrylate. A copolymer formed from at least one structural unit of a derivative.

In some embodiments, the resin (B) may account for about 5-25 wt % of the colored resin composition, preferably 6-15 wt %, more preferably 6-10 wt %.

In some embodiments, the photopolymerizable monomer (C) is a monomer that can be polymerized by reactive radicals and/or acids generated by the photopolymerization initiator (D), such as, but not limited to, polymerizable ethylene. Sexually unsaturated bonds, such as (meth)acrylate compounds. Here, the compound described using parentheses means including the presence or absence of the characters in the parentheses, such as the aforementioned (meth)acrylate compound, the case of including an acrylate compound, and a methacrylate compound. The photopolymerizable monomer (C) may also be referred to as a polymerizable compound.

For example, the photopolymerizable monomer (C) may include, but is not limited to, at least one selected from the group consisting of: nonylphenyl carbitol acrylate, 2-hydroxy- 3-phenoxypropyl ester, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and other polymerizable compounds having one ethylenically unsaturated bond; bis(methyl) 1,6-hexanediol acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A Polymerizable compounds having two ethylenically unsaturated bonds such as bis(acryloyloxyethyl) ether and 3-methylpentanediol di(meth)acrylate; and trimethylol tri(meth)acrylate propane, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate Esters, tripentaerythritol hepta(meth)acrylate, pentaerythritol ten(meth)acrylate, pentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanate, tetrakis(meth)acrylate (Meth) ethylene glycol modified pentaerythritol, ethylene glycol hexa(meth)acrylate modified dipentaerythritol, propylene glycol tetra(meth)acrylate modified pentaerythritol, propylene glycol hexa(meth)acrylate modified di-pentaerythritol A polymerizable compound having three ethylenically unsaturated bonds, such as pentaerythritol ester, caprolactone tetra(meth)acrylate-modified pentaerythritol, and caprolactone hexa(meth)acrylate-modified dipentaerythritol. In some embodiments, the photopolymerizable monomer (C) is, for example, a compound having an ethylenically unsaturated double bond. In some embodiments, the photopolymerizable monomer (C) is, for example, a polymerizable compound having three ethylenically unsaturated double bonds.

Commercially available products of the photopolymerizable monomer (C) include KAYARAD (registered trademark) DPHA (Nihon Kayaku Co., Ltd.), A-TMM-3LM-N (Shin Nakamura Chemical Industry Co., Ltd.), and A9500 (Shin Nakamura Chemical Industry Co., Ltd.) ).

The weight average molecular weight of the photopolymerizable monomer (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

The content of the photopolymerizable monomer (C) is preferably 7 to 65 parts by weight, more preferably 13 to 60 parts by weight, and even more preferably 17 to 55 parts by weight based on 100 parts by weight of the solid component. If the content of the photopolymerizable monomer (C) is within the above-mentioned range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter can be improved.

According to some embodiments, the photopolymerization initiator (D) can be any compound that can generate active radicals, acids, etc. by the action of light, thereby starting the photopolymerization reaction, and is not particularly limited.

In some embodiments, the photopolymerizable monomer (C) may account for about 1-10 wt % of the colored resin composition.

For example, the photopolymerization initiator (D) may include, but is not limited to, at least one selected from the group consisting of: O-acyloxime (O-acyloxime) compound, alkyl group Phenyl ketone compound, bisimidazole compound, triazine compound, acyl phosphine oxide, benzoin compound, diphenyl ketone compound, quinone compound, 10-butyl-2-chloroacridone, benzyl base, methyl phenylformate, acetophenone, and titanocene compounds.

In some embodiments, the photopolymerization initiator (D) preferably comprises at least one selected from the group consisting of: O-acyl oxime compounds, alkyl phenyl ketone compounds, bis Imidazole compounds, acetophenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds. For example, in the case of using an O-acyl oxime compound as the photopolymerization initiator (D), Irgacure® OXE-01 (BASF Corporation), Irgacure® OXE-02 (BASF Corporation), N-1919 ( ADEKA Corporation) and other commercially available products.

The above-mentioned O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bonding end.

Examples of the above-mentioned O-acyl oxime compound include N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, Oxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)- 3-Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3 -yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxolatylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6- (2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as IRGACURE OXE01 and OXE02 (the above are manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) can be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, yl-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -At least one of cyclopentylpropan-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one- 2-Imine. In the case of these O-acyl oxime compounds, a high-brightness color filter tends to be obtained.

The above-mentioned alkyl phenyl ketone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

As a compound having a partial structure represented by formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl base]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercially available products such as IRGACURE 369, 907, and 379 (the above are manufactured by BASF Corporation) can be used.

As a compound having a partial structure represented by formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4- (2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Oligomers of ketones, α,α-diethoxyacetophenone, benzalkonium dimethyl ketal, etc.

In terms of sensitivity, as the alkyl phenyl ketone compound, a compound having a partial structure represented by the formula (d2) is preferable.

Examples of the above-mentioned triazine compound include 2,4-bis-trichloromethyl-6--4-methoxyphenyl-1,3,5-triazine, 2,4-bis-trichloromethyl-6 -4-Methoxynaphthyl-1,3,5-triazine, 2,4-bistrichloromethyl-6-pipronyl-1,3,5-triazine, 2,4-bistrichloromethane yl-6-4-methoxystyryl-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(5-methylfuran-2-yl)vinyl ]-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4- Bistrichloromethyl-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bistrichloromethyl- 6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

As said acyl phosphine oxide compound, 2, 4, 6- trimethylbenzyl diphenyl phosphine oxide etc. are mentioned. Commercially available products such as IRGACURE (registered trademark) 819 (manufactured by BASF) can be used.

As said biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62- 174204 Gazette, etc.), imidazole compounds in which the phenyl group at the 4,4', 5,5'-position is substituted with an alkoxycarbonyl group (for example, see Japanese Patent Laid-Open No. 7-10913, etc.), and the like.

Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Esters, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(3-butylperoxycarbonyl) Benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthraquinone, 2-ethylanthraquinone and camphorquinone; 10-butyl- 2-Chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. Preferably, these polymerization initiators may be used in combination with a polymerization initiator (especially amines) described later.

The acid generators include 4-hydroxyphenyldimethyl perylene-p-toluenesulfonate, 4-hydroxyphenyldimethyl perylene hexafluoroantimonate, and 4-acetoxyphenyldimethylene Acetyl-p-toluenesulfonate, 4-Acetyloxyphenylmethylbenzyl-hexafluoroantimonate, triphenyl-p-toluenesulfonate, triphenyl-perylene hexafluoroantimonate , Diphenyliodonium-p-toluenesulfonate, onium salts such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

The content of the polymerization initiator may be 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, if the total of the resin (B-2) and the polymerizable compound is 100 parts by weight share. If the content of the polymerization initiator is within the above-mentioned range, the sensitivity will be increased and the exposure time will tend to be shortened, so that the productivity of the color filter can be improved.

In some embodiments, the photopolymerization initiator (D) may account for about 0.1-2.5 wt % of the colored resin composition.

In some embodiments, solvent (E) may include, but is not limited to, at least one selected from the group consisting of: an ester solvent (herein meant to contain -COO- in the molecule but not -O- solvent), ether solvent (here means a solvent containing -O- but not -COO- in the molecule), ether ester solvent (here means containing -COO- and -O- in the molecule solvent), ketone solvent (here means a solvent containing -CO- but not -COO- in the molecule), alcohol solvent (here means containing OH in the molecule but not -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol diethylene glycol Butyl ether, anisole, phenethyl ether and methyl anisole, etc.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

As the aromatic hydrocarbon solvent, benzene, toluene, xylene, 1,3,5-trimethylbenzene and the like can be mentioned.

As an amide solvent, N,N- dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. are mentioned.

Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120° C. or higher and 180° C. or lower is preferable from the viewpoint of coatability and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate , propylene glycol monomethyl ether, N-methylpyrrolidone, ethyl lactate and ethyl 3-ethoxypropionate.

The content rate of the solvent may be 70 to 95% by weight, more preferably 80 to 90% by weight, relative to the total amount of the colored resin composition of the present invention. In other words, the total content of the solid components of the colored resin composition may be 5 to 30% by weight, more preferably 10 to 20% by weight. When the content of the solvent is within the above-mentioned range, the flatness at the time of coating becomes favorable, and the color density does not become insufficient when the color filter is formed, so that the display characteristics tend to become favorable.

In some embodiments, solvent (E) may comprise a first solvent having a higher boiling point and a second solvent having a lower boiling point. In some embodiments, the boiling point of the first solvent is, for example, 150°C to 230°C, and the boiling point of the second solvent is lower than 150°C. In some embodiments, the first solvent accounts for 1 wt % to 40 wt % of the solvent (E), preferably 5 to 30 wt %, more preferably 10 to 25 wt %.

In some embodiments, the first solvent is, for example, cyclohexanone (CHN), and the second solvent is, for example, propylene glycol monomethyl ether acetate (PGMEA).

According to some embodiments of the present disclosure, using the aforementioned combination of a solvent with a boiling point higher than 150°C and a solvent with a boiling point lower than 150°C can improve the stability and heat resistance of the dye molecules, thereby making the coloring resin composition possible. The coating can have good color rendering effect.

In some embodiments, the solvent (E) comprising the aforementioned first solvent and the second solvent may account for about 75-90 wt % of the colored resin composition.

In some embodiments, the colored resin composition may further include antioxidants. In some embodiments, the antioxidant may include phenolic type compounds and/or bisphenolic type compounds, but is not limited thereto.

In some embodiments, the colored resin composition may further include a leveling agent (F). Leveling agent (F) is a commonly used coating additive, which can promote the formation of a smooth, smooth and uniform coating film during the drying process of the coating. As a leveling agent, a silicone-based surfactant, a fluorine-based surfactant, a silicone-based surfactant having a fluorine atom, and the like are exemplified. These may have a polymerizable group in the side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray-Dow Corning Corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 ( manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd. (LLC)), and the like.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray-Dow Corning Corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 ( manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd. (LLC)), and the like.

As said fluorochemical surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, FLUORAD (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (DIC Co., Ltd.), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), SURFLON (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd. ) and E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.), etc.

As the organosilicon-based surfactant having the above-mentioned fluorine atom, a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like can be exemplified. Specifically, MEGAFACE (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Co., Ltd.), etc. are mentioned.

The content of the leveling agent may be 0.001% by weight or more and 0.2% by weight or less, preferably 0.002% by weight or more and 0.1% by weight or less, more preferably 0.005% by weight, based on the total amount of the colored resin composition. more than 0.05 wt % or less.

In some embodiments, the colored resin composition may further include other additives such as surfactants, polymerization initiation assistants, fillers, adhesion promoters, light stabilizers, etc., but is not limited thereto.

A polymerization initiator is a compound or a sensitizer for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator. When a polymerization initiator is included, it is usually used in combination with a polymerization initiator. As a polymerization initiation aid, an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine; 4, 4'-bis(dimethylamino)benzophenone (commonly known as MichleRketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl) among them, 4,4'-bis(diethylamino)benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

As said alkoxyanthracene compound, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, and dimethylphenylsulfanyl acetic acid. Alkyl Acetic Acid, Methoxyphenylsulfanyl Acetic Acid, Dimethoxyphenylsulfanyl Acetic Acid, Chlorophenylsulfanyl Acetic Acid, Dichlorophenylsulfanyl Acetic Acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

In the case of using these polymerization initiators, the content of the polymerization initiator may be 100 parts by weight of the total of the resin (B-2) and the photopolymerizable monomer (C) (polymerizable compound). 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight. If the amount of the polymerization initiation aid is within this range, a colored pattern can be formed with a further high sensitivity, and the productivity of the color filter tends to be improved.

Another embodiment of the present disclosure is directed to a color filter formed from the colored resin composition according to any of the foregoing embodiments. For example, the coloring resin composition according to any of the foregoing embodiments can be used to form the color filter by a photolithography method, an inkjet method, or a printing method, but the present disclosure is not limited thereto.

As a method of producing a color filter (color filter pattern) from the coloring resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, the photolithography method is preferable. The photolithography method is a method in which the above-mentioned colored resin composition is applied to a substrate, dried to form a colored composition layer, and developed by exposing the colored composition layer through a photomask. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask and/or not developing during exposure. The colored pattern and colored coating film thus formed can be used as the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose, application, etc., for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass whose surface is coated with silica, polycarbonate, polymethyl methacrylate, polyparaphenylene can be used Resin sheets such as ethylene dicarboxylate, silicon, and aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above-mentioned substrates. Additional color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of various-color patterns (pixels) by photolithography can be performed under known or conventional apparatus and conditions. For example, it can be produced as follows.

First, the colored curable resin composition is applied on a substrate, and dried by heating (prebaking) and/or under reduced pressure to remove volatile components such as a solvent and dry to obtain a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned.

Next, the coloring composition layer is exposed to light through a photomask for forming a target coloring pattern. It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since parallel light rays can be uniformly irradiated to the whole exposure surface, and a photomask and the board|substrate on which the coloring composition layer is formed can be correctly aligned.

A coloring pattern is formed on a board|substrate by making the exposed coloring composition layer contact with a developing solution, and developing. By developing, the unexposed portion of the coloring composition layer is dissolved in the developing solution and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight. Furthermore, the developer may contain a surfactant. The development method may be any of a spin dipping method, a dipping method, a spray method, and the like. Furthermore, the substrate can be inclined at an arbitrary angle during development. It can be washed with water after developing.

The dose of the aforementioned exposure procedure is not particularly limited, but since the colored resin composition of the present application contains the first colorant and the resin (B-2), it can be applied to a higher exposure dose, and a fine hole pattern can still be obtained. In some embodiments, the present case can be exposed with an exposure dose of 50 to 100 mJ. In some embodiments, the gap between the edge of the hole and the hole after exposure and development may be only 1 to 50 μm, or may be 3 to 40 μm.

Furthermore, it is preferable to post-bake the obtained coloring pattern. The post-baking temperature is preferably 90°C to 250°C, or may be 100°C to 240°C. The post-baking time is preferably 1 to 120 minutes.

With the colored resin composition of the present application, a color filter with a fine hole pattern can be produced. This color filter can be used as a color filter or a color filter for display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state photographing elements.

Yet another embodiment of the present disclosure relates to a display device, which may include the aforementioned color filter, but the present disclosure is not limited thereto. According to some embodiments of the present disclosure, the display device may be a display such as a liquid crystal display device, an organic electroluminescence display device, or a plasma display device.

For example, the display device may have a backlight, a TFT substrate, a color filter substrate, and a display medium (such as liquid crystal) disposed between the TFT substrate and the color filter substrate, and the color filter substrate of which can use the A filter formed of a colored resin composition.

Hereinafter, the present disclosure will provide several examples and comparative examples to more specifically illustrate the effects that can be achieved by the coloring resin composition according to the embodiments of the present disclosure, and the color photoresist composition obtained by applying the present disclosure. properties of things. However, the following examples and comparative examples are only used for illustration, and should not be construed as a limitation of the implementation of the present disclosure. The compositions of the following examples and comparative examples are shown in Tables 1 to 3, wherein the selected types of each component are described below. The unit "parts" used below means parts by weight unless otherwise specified.

[Preparation Example A1 - Preparation of First Colorant A1-1]

式(A1-1-i)The following reactions were carried out under nitrogen atmosphere. After putting 32.2 parts of potassium thiocyanate and 160 parts of acetone into a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Next, 50 parts of 2-fluorobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, after cooling the reaction mixture with ice, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After the dropwise addition, the reaction mixture was further stirred at room temperature for 30 minutes. Next, 31.3 parts of chloroacetic acid was added dropwise to the reaction mixture at room temperature. After completion of the dropwise addition, the reaction mixture was stirred under reflux with heating for 7 hours. Next, after cooling the reaction mixture to room temperature, the reaction mixture was poured into 120 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped, and it was left to stand for 30 minutes, and was separated into an organic layer and an aqueous layer. After discarding the aqueous layer by the liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dry organic layer. The obtained organic layer was solvent-distilled with an evaporator, and the pale yellow liquid was obtained. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60° C. to obtain 49.9 parts of a compound represented by formula (A1-1-i). The yield was 51%.

Formula (A1-1-i)

式(A1-1-ii)The following reactions were performed under a nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide into a flask equipped with a cooling pipe and a stirring device, the mixed solution was cooled with ice. After adding 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) little by little over 30 minutes under ice-cooling, it stirred for 1 hour while warming up to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction mixture, and the mixture was stirred at room temperature for 24 hours. After the reaction mixture was added little by little to 200 parts of ice water, the mixture was allowed to stand at room temperature for 15 hours, and the water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to this viscous solid, it stirred at room temperature for 15 hours. After the precipitated solid was separated by filtration, it was purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60° C. to obtain 9.8 parts of a compound represented by formula (A1-1-ii). The yield was 53%.

Formula (A1-1-ii)

式(A1-1-iii)The following reactions were performed under a nitrogen atmosphere. After putting 8.2 parts of the compound represented by the formula (A1-1-i), 10 parts of the compound represented by the formula (A1-1-ii), and 20 parts of toluene into a flask equipped with a cooling pipe and a stirring device, oxychlorination was added. 12.2 parts of phosphorus was stirred at 95°C to 100°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropanol. Next, after pouring the diluted reaction mixture into 300 parts of saturated brine, 100 parts of toluene was added, followed by stirring for 30 minutes. Then, stirring was stopped, and it was left to stand for 30 minutes, and was separated into an organic layer and an aqueous layer. After discarding the aqueous layer by the liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, the mixture was filtered to obtain an organic layer. The obtained organic layer was solvent-distilled with an evaporator, and the blue-purple solid was obtained. Furthermore, the blue-violet solid was dried under reduced pressure at 60° C. to obtain 18.4 parts of the compound represented by the formula (A1-1-iii). The yield was 100%.

Formula (A1-1-iii)

式(A1-1)The following reactions were performed under nitrogen atmosphere. 2.0 parts of the compound represented by formula (A1-1-iii) and 167 parts of ion-exchanged water were added to a flask equipped with a cooling pipe and a stirring device, and the mixture was stirred at 40° C. for 30 minutes. 5.8 parts of barium chloride dihydrate and 35 parts of ion-exchanged water were added to the beaker, followed by stirring for 30 minutes. To the aqueous solution of the compound represented by the formula (A1-1-iii) previously prepared, the aqueous barium chloride solution was dropped while maintaining the liquid temperature of the aqueous solution at 40° C., followed by stirring for 1 hour and 20 minutes. The obtained reaction suspension was filtered, and the solid collected by filtration was suspended and washed with 67 parts of ion-exchanged water, and then washed with 20 parts of ion-exchanged water. The obtained solid was dried under reduced pressure at 60° C. to obtain 1.9 parts of a compound represented by formula (A1-1). The yield was 89%.

Formula (A1-1)

[Preparation Example A2 - Preparation of First Colorant A1-2]

式(A1-2-iii)The compound represented by the formula (A1-2-iii) was obtained in the same manner as in Preparation Example A1 except that the compound represented by the formula (A1-1-ii) was changed to the compound represented by the formula (A1-2-ii) . In addition, in the formula, -SO ₃ ^- means that any one of the hydrogen atoms contained in the partial structure in parentheses is substituted.

Formula (A1-2-iii)

式(A1-2)Then, (A1-1-iii) in Preparation Example A1 is changed to the compound of formula (A1-2-iii) to obtain the compound of formula (A1-2).

Formula (A1-2)

[Preparation Example A3 - Preparation of Second Colorant A2-1]

Into a flask equipped with a condenser tube and a stirring device, 15 parts of pigments (manufactured by Sinochem Chemicals), 150 parts of chloroform, and 8.9 parts of N,N-dimethylformamide represented by the formula (A2-1-i) were put, and stirred. Next, 10.9 parts of sulfite chloride was added dropwise while maintaining the temperature at 20° C. or lower. After completion of the dropwise addition, the temperature was raised to 50° C., the reaction was maintained at the same temperature for 5 hours, and thereafter, the temperature was cooled to 20° C. While maintaining the reaction solution after cooling at 20° C. or less under stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. The reaction was carried out by stirring at the same temperature for 5 hours. Next, the solvent of the obtained reaction mixture was distilled off using a rotary evaporator, and a small amount of methanol was added, followed by vigorous stirring. While stirring, this mixture was added to a mixed solution of 375 parts of ion-exchanged water to precipitate crystals. The precipitated crystals are separated by filtration, carefully washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain formula (A2-1) (the mixture of dye A2-1-a～dye A2-1-h) 11.3 servings:

[Preparation Example A4 - Preparation of Second Colorant A2-2]

式(A2-2)It was prepared according to the method described in Example 1 of JP 2016-27075 to obtain the compound of formula (A2-2).

Formula (A2-2)

[Preparation Example A5 - Preparation of Second Colorant A2-3]

式(A2-3)It was prepared according to the method described in Synthesis Example 2 of JP 2016-176075 to obtain the compound of formula (A2-3).

Formula (A2-3)

(1) Resin material-1: self-synthesized, please refer to Preparation Example 1 below.

[Preparation Example 1]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, a mixture of 20.0 g (0.20 moles) of methyl methacrylate, 88.0 g (0.40 moles) of tricyclodecyl methacrylate and 34.4 (0.4 moles) of methacrylic acid was prepared. To the obtained monomer mixture, 4.0 g of t-butylperoxy-2-ethylhexanoate was added, and dropped into the aforementioned flask from a dropping funnel. After the dropping was completed, the copolymer was produced by stirring at 95° C. for 3 hours to carry out a copolymerization reaction. Next, after replacing the inside of the flask with air, 42.6 g (0.3 moles) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added ), carry out ring-opening addition reaction at 120 ℃ for 6 hours, manufacture copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution with a solid content concentration of 30 mass % (solid content acid value 30 mgKOH/g, weight average molecular weight 37,100). The copolymer (resin material-1) produced in Preparation Example 1 has a structural unit represented by the following Chemical Formula 4. [Chemical formula 4]

(2) Resin material-2: self-synthesized, please refer to the following preparation examples 2-1~2-2. Resin B2-1 of Preparation Example 2-1 and Resin B2-2 of Preparation Example 2-2 can be used as resin material-2 either by choice or in combination.

[Preparation Example 2-1: Preparation of Resin B2-1]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was allowed to flow to make it a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and heated to 85°C while stirring. Next, 19 parts of methacrylic acid (for forming the structural unit on the lower left side) and acrylic acid 3,4-epoxytricyclo[5.2.1.02,6] were dropped into the flask using a dropping pump for about 5 hours. A mixture of decane-8-yl ester and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate (the content ratio is 50:50 in molar ratio) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) 171 parts were dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in propylene glycol monolayer was added dropwise to the flask using another dripping pump for about 5 hours. A solution of 120 parts of methyl ether acetate. After the drop of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of the copolymer (resin B2-1) with a solid content of 43.5%. The weight-average molecular weight of the obtained resin B2-1 was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH/g. The copolymer prepared in Preparation Example 2-1 has a structural unit represented by the following Chemical Formula 5-1. [Chemical formula 5-1]

[Preparation Example 2-2: Preparation of Resin B2-2]

The flask equipped with a reflux condenser, a dropping funnel, and a stirrer was replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02]6)decane-9- 289 parts of propylene glycol monomethyl ether acetate and 125 parts of mixed solutions of propylene glycol monomethyl ether acetate were dripped over 5 hours to the mixture of acrylic acid ester (the content ratio was 1:1 in molar ratio). On the other hand, a solution in which 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the mixture was kept at 80° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin B2-2) solution with a solid content of 35.1% and a viscosity of 125 mPas measured by a Brookfield viscometer (23° C.). . The weight average molecular weight (Mw) of the obtained copolymer was 9.2×10 ³ , the molecular weight distribution (Mw/Mn) was 2.08, and the acid value (solid content conversion value) was 77 mgKOH/g. The copolymer prepared in Preparation Example 2-2 has a constituent unit shown in the following Chemical Formula 5-2. [Chemical formula 5-2]

(3) Resin material-3: self-synthesized, please refer to the following preparation examples 3-1~3-2. Resin B3-1 of Preparation Example 3-1 and Resin B3-2 of Preparation Example 3-2 can be used as resin material-3 either by choice or in combination.

[Preparation Example 3-1: Preparation of Resin B3-1]

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 700.0 g of propylene glycol monomethyl ether was added, and the temperature was raised to 88° C. with stirring while replacing with nitrogen. Next, in a mixture of 46.2 g (0.54 mol) of methacrylic acid, 60.5 g (0.24 mol) of 3-methacryloyloxypropyltrimethoxysilane and 166.0 g (1.66 mol) of methyl methacrylate To the obtained monomer mixture, 27.3 g of 2,2'-azobis(isobutyric acid) dimethyl ester (polymerization initiator) was added, and the resultant was dropped into the aforementioned flask from a dropping funnel. After the dropwise addition, the copolymerization reaction was carried out with stirring at 88° C. for 5 hours to obtain resin B3-1 (weight average molecular weight: 7100, molecular weight distribution (Mw/Mn): 2.1, acid value: 99 KOHmg/g, silane group equivalent: 1230 g/mol).

[Preparation Example 3-2: Preparation of Resin B3-2]

The preparation method is roughly the same as that of Preparation Example 3-1, except that 3-methacryloyloxypropyltrimethoxysilane is replaced by 68.3 g of 3-methacryloyloxypropyltriethoxysilane, Resin B3-2 was obtained.

(4) Photopolymerizable monomer: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) was used.

(5) Photopolymerization initiators: acetophenone compound (trade name: Trolly PBG327) and O-acyl oxime compound (trade name: BASF OXE-01).

(6) Colorant: In the examples in Table 1, C.I Pigment Blue 15:6 and the aforementioned oxonone dye were used as colorants; in the examples in Tables 5 to 6, the first one of the aforementioned preparation examples was used Colorants and/or Secondary Colorants.

(7) Leveling agent: polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.).

(8) Solvent: In the examples in Table 1, a mixed solvent of 20 wt% cyclohexanone (CHN) and 80 wt% propylene glycol monomethyl ether acetate (PGMEA) was used; in Tables 5-6 In the examples, propylene glycol monomethyl ether acetate (PGMEA) was used.

Table 1 (the numbers in the table are the proportion by weight of each composition) Colorant resin photopolymerizable monomer photopolymerization initiator leveling agent solvent Example 1 4.4 6.6 3.6 2.39 0.01 83 Example 2 4.4 6.9 3.7 1.99 0.01 83 Example 3 4.4 7.0 3.9 1.69 0.01 83 Comparative Example 1 4.4 6.7 3.6 2.29 0.01 83 Comparative Example 2 4.4 7.1 4.0 1.49 0.01 83 Comparative Example 3 4.4 6.7 3.2 2.83 0.01 83

Table 2 (the numbers in the table are the weight percentages of each resin material in the resin of this example or comparative example) Resin material-1 Resin material-2 (including EDCPA) Resin material-3 (containing silane group) Example 1 0% 67% 33% Example 2 0% 66% 34% Example 3 0% 75% 25% Comparative Example 1 45% 55% 0% Comparative Example 2 0% 100% 0% Comparative Example 3 67% 0% 33%

table 3 The ratio of the number of EDCP monomer units to the total number of all monomer units in the resin The parts by weight of silane-based monomer units relative to 100 parts by weight of EDCP monomer units The number of EDCP monomer units: the number of silane-based monomer units Example 1 12.2 4.75 1:0.054 Example 2 27.6 5.47 1:0.056 Example 3 41.3 3.82 1:0.038 Comparative Example 1 10.5 0 N/A Comparative Example 2 43.1 0 N/A Comparative Example 3 0 N/A N/A

The prepared colored resin composition was coated on a 5cm*5cm glass substrate (Eagle2000, Corning Company) by spin coating, with a coating thickness of about 1.5 microns (µm) to 4.5 microns, and then at 100 ^o C Pre-bake for 3 minutes. After being left to cool, exposure machine (TME-150RSK, manufactured by TOPCON Co., Ltd.) was used to irradiate with light at an exposure amount of 80 mJ/ ^cm2 (365 nm reference) in an atmospheric environment, and a series of exposures and Development process to form a sample of patterned color filters. Then post-bake at 230 ^o C in an oven for 60 minutes to obtain a sample of the color filter, and measure the volume shrinkage rate of the sample, and determine the adhesion of the color filter to the glass substrate. The results of each of the following examples and comparative examples are shown in Table 4.

Table 4 Volume shrinkage adhesion Example 1 9.3% good Example 2 8.2% Excellent Example 3 7.4% Excellent Comparative Example 1 19.7% Difference Comparative Example 2 21.1% fall off Comparative Example 3 16.1% Difference

As shown in Table 4, when the coloring resin composition of the examples other than the present disclosure is used, as shown in the results of Comparative Examples 1 to 3, when the coloring resin composition does not contain EDCP monomer units, the formed color The volume shrinkage rate of the filter is quite large, which also makes the color filter and the glass substrate not well attached together, so the formed sample of the overall structure has poor heat resistance and stability.

As shown in Tables 3 to 4, the samples of the color filters formed from the colored resin compositions of the respective Examples all had good heat resistance and stability. For example, in Example 3, when the ratio of the number of EDCP monomer units is greater than 40%, the prepared color filter has very low shrinkage rate and excellent adhesion.

The components were mixed in the parts by weight shown in Table 5 below to obtain a colored resin composition, and the following Examples and Comparative Examples were carried out with 18 parts by weight of solid components and 82 parts by weight of solvent.

[Production of Color Filters]

On a 2-inch square glass substrate (# 1737; manufactured by Corning), the coloring resin composition prepared in accordance with the composition formula in Table 5 was applied by spin coating, and then carried out at 100°C. The coloring composition layer was formed by prebaking for 3 minutes. After cooling, use an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.), and use a photomask (a hole spacing of about 40 μm-80 μm) to expose in an atmospheric environment with a predetermined exposure amount (365 nm reference). The coloring composition layer after exposure was post-baked in an oven at 230° C. for 20 minutes to prepare a color filter (film thickness: 2.8 μm).

[Integrity evaluation of hole pattern]

Each optical filter formed above was observed with an optical microscope to observe whether a hole pattern was formed on the optical filter, and the results were recorded in Tables 5 to 6.

table 5 Comparative Example A1 Comparative Example A2 Example A1 Example A2 Example A3 first colorant A1-1 2.1 2.1 2.1 2.1 A1-2 2.1 secondary colorant A2-1 0.1 0.1 0.1 0.1 0.1 A2-2 A2-3 Resin (B-2) B1-1 9.3 9.3 B1-2 9.3 Resin (B-1) B2-1 9.3 B2-2 9.3 polymeric compound 5.7 5.7 5.7 5.7 5.7 polymerization initiator 0.9 0.9 0.9 0.9 0.9 leveling agent 0.01 0.01 0.01 0.01 0.01 Integrity evaluation of hole pattern Exposure (mJ) 20 O O O O O 50 X X O O O 75 X X O O O 100 X X O O O

Table 5 (continued) Example A4 Example A5 Example A6 Example A7 Example A8 first colorant A1-1 2.1 2.1 2.1 A1-2 2.1 2.1 secondary colorant A2-1 A2-2 0.1 0.1 A2-3 0.1 0.1 Resin (B-2) B1-1 9.3 9.3 9.3 9.3 9.3 B1-2 Resin (B-1) B2-1 B2-2 polymeric compound 5.7 5.7 5.7 5.7 5.7 polymerization initiator 0.9 0.9 0.9 0.9 0.9 leveling agent 0.01 0.01 0.01 0.01 0.01 Integrity evaluation of hole pattern Exposure (mJ) 20 O O O O O 50 O O O O O 75 O O O O O 100 O O O O O

Table 6 Example A9 Example A10 Example A11 Example A12 Example A13 first colorant A1-1 2.1 2.1 2.1 2.1 2.1 A1-2 secondary colorant A2-1 0.1 0.1 0.1 0.1 0.1 A2-2 A2-3 Resin (B-2) B1-1 7.0 4.7 2.3 13.0 2.2 B1-2 Resin (B-1) B2-1 2.3 4.6 7.0 B2-2 polymeric compound 5.7 5.7 5.7 5.7 5.7 polymerization initiator 0.9 0.9 0.9 0.9 0.9 leveling agent 0.01 0.01 0.01 0.01 0.01 Integrity evaluation of hole pattern Exposure (mJ) 20 O O X O O 50 O O X O O 75 O X X O O 100 O X X X X

Table 6 (continued) Example A14 Example A15 Example A16 Example A17 Example A18 Example A19 first colorant A1-1 2.1 2.1 2.1 2.1 2.1 2.1 A1-2 secondary colorant A2-1 0.1 0.1 0.1 0.1 0.1 0.1 A2-2 A2-3 Resin (B-2) B1-1 14.0 1.8 B1-2 13.0 2.3 13.9 1.8 Resin (B-1) B2-1 B2-2 polymeric compound 5.7 5.7 5.7 5.7 5.7 5.7 polymerization initiator 0.9 0.9 0.9 0.9 0.9 0.9 leveling agent 0.01 0.01 0.01 0.01 0.01 0.01 Integrity evaluation of hole pattern Exposure (mJ) 20 O O O O O O 50 O O O O O O 75 X X O O X X 100 X X X X X X

It can be seen from the comparative examples A1 and A2 in Table 5 that when the colored resin composition does not contain the silicon-containing resin (B-2) of this case, although a clear hole pattern can still be formed at a low exposure dose, when exposed to light, a clear hole pattern can still be formed. As the dose increases, fine hole patterns cannot be formed.

It can be seen from Examples A1 and A2 that the colored resin compositions containing different silicon-containing resins B1-1 and B1-2 still have the effects described in this case.

It can be seen from Examples A3-A8 that the use of different first colorants or the use of different second colorants does not affect the formation of the hole pattern of the subsequently formed color filter under high exposure dose. For example, Examples A1, A3 using different first colorants; or Examples A1, A5, A7 using different second colorants, and Examples A3, A6, A8, can still be used at high exposure doses A good hole pattern is formed.

However, as shown in Example A4, the colored resin composition without the use of the second colorant can still have the effect described in this case.

See Table 2 next. As is clear from Example A9 in Table 2, the colored resin composition may contain both the resin (B-1) and the resin (B-2). However, if the weight ratio of resin (B-1) to solid components is greater than the weight ratio of resin (B-2) to solid components (for example, in Example A10, the total weight of resin (B-1) is the total weight of resin (B-1). 2) more than 50% of the total weight), the performance of the colored resin composition under high exposure doses will be affected.

From Examples A12, A14, and Examples A13 and A15 in Table 2, it can be seen that when the resin (B-2) occupies a certain weight ratio range of the solid component, it can have the best effect. When the resin (B-2) accounts for more than 60 wt % and less than 20 wt % of the solid component, the performance of the colored resin composition under high exposure doses will be affected.

From Examples A16 to A19, it can be seen that the preferred range of different resins (B-2) (eg, the first resin B1-2) is also similar to that of the resin B1-1.

In summary, by including the silicon-containing resin described in this application in the colored resin composition, the layer formed by the colored resin composition can be formed with fine and good fineness even under high exposure. Hole pattern.

Although the present disclosure is disclosed in the foregoing embodiments, it is not intended to limit the present disclosure. Those with ordinary knowledge in the technical field to which the present disclosure pertains may make some changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the protection scope of this disclosure should be determined by the scope of the appended patent application.

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Claims (9)

A coloring resin composition, comprising: a coloring agent of more than 3wt%; a resin of 5-25wt%, including epoxy dicyclopentenyl (epoxy dicyclopentenyl) monomer units and silane-based monomer units; 1-10wt% of light A polymerized monomer; 0.1-2.5 wt % of a photopolymerization initiator; and 75-90 wt % of a solvent; wherein the epoxydicyclopentenyl monomer unit includes a first monomer having a structure as shown in Chemical Formula 1 At least one of the monomer unit and the second monomer unit having the structure shown in Chemical Formula 2:

Wherein, R1 represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group, and X1 represents a single bond, -R3-, -R3-O-, -R3- S-, or -R3-NH-, wherein R3 represents an alkylene group having 1 to 6 carbon atoms, and n is a positive integer; [Chemical formula 2]

Wherein, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group, and X2 represents a single bond, -R3-, -R3-O-, -R3- S-, or -R3-NH-, m is a positive integer; wherein the silyl monomer unit has the structure shown in Chemical Formula 3:

Wherein, R4 represents a hydrogen atom or a methyl group; R5~R7 independently represent a hydrogen atom, an alkyl group with 1~6 carbon atoms or an alkoxy group with 1~6 carbon atoms, but at least one of R5~R7 is a carbon number 1-6 alkoxy groups; p is a positive integer, q is an integer of 1-10. The colored resin composition according to item 1 of the claimed scope, wherein the number of the epoxy dicyclopentenyl monomer units accounts for 8% to 50% of the total monomer units of the resin. The colored resin composition according to claim 1, wherein the ratio of the number of the epoxy dicyclopentenyl monomer units to the number of the silane group monomer units is 1:0.02~1:0.08 . The colored resin composition of claim 1, wherein the silane-based monomer unit is 2 to 8 parts by weight relative to 100 parts by weight of the epoxydicyclopentenyl monomer unit . The colored resin composition of claim 1, wherein the epoxydicyclopentenyl monomer unit includes a monomer unit having a structure shown in Chemical Formula 1A and a monomer unit having a structure shown in Chemical Formula 2A The monomer unit of:

. The colored resin composition as described in item 1 of the claimed scope, wherein the silane-based monomer unit has the structure shown in Chemical Formula 3A or Chemical Formula 3B:

The colored resin composition according to item 1 of the claimed scope, wherein the solvent comprises a first solvent and a second solvent, the boiling point of the first solvent is 150°C to 230°C, and the second solvent has a boiling point of 150°C to 230°C. The boiling point is lower than 150° C., wherein the first solvent accounts for 1wt% to 40wt% of the solvent. A color filter is formed from the colored resin composition described in any one of the first to seventh claims in the scope of application. A display device comprising the color filter as described in item 8 of the patent application scope.