KR20210008314A - Coloring resin composition, and color filter and display device using the same - Google Patents

Abstract

Provided are a coloring resin composition, and a color filter and a display device using the same. One embodiment of the present invention provides a coloring resin composition, and a color filter and a display device using the same. The coloring resin composition contains a colorant, a resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent. The resin contains an epoxy dicyclopentenyl (EDCP) monomer unit shown below and a silane monomer unit. According to the present invention, deformation of a coating layer of the coloring resin composition caused by a high-temperature process can be suppressed.

Description

A colored resin composition, and a color filter and a display device using the same TECHNICAL FIELD [0002]

The present disclosure relates to a colored resin composition. The present disclosure also relates to a color filter formed by the colored resin composition. The present disclosure also relates to a display device comprising a corresponding color filter.

In general, a display device controls the color of each pixel using a color filter. For example, in a relatively early liquid crystal display device, a color filter is formed on a substrate opposite to a thin film transistor substrate, and the entire structure of this substrate and the color filter provided therein is usually referred to as a color filter substrate. A photoresist structure of a color filter can be formed using a resin composition.

In general, in order to cope with various types of display devices, components of a colored resin composition are adjusted and optimized to realize formation of a color filter having various predetermined characteristics.

A colored resin composition and a color filter and display device using the same are provided.

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 resin includes an epoxy dicyclopentenyl (EDCP) monomer unit and a silane monomer unit.

According to a further embodiment of the present disclosure, a colored resin composition is provided. The colored resin composition contains a solid component and a solvent. Among these, the solid component includes a first colorant, a first resin, a polymerizable compound, and a polymerization initiator. The first colorant is a compound represented by the following formula (I):

The first resin contains the structural unit (b1-1) represented by the following formula (1b):

R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ in formula (I), T ¹ , k, M, r; R4 to R7, p, and q in formula (1b) are as defined in the present specification.

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

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

The present disclosure relates to a colored resin composition and a color filter and a display device using the same. The resin of the colored resin composition of the embodiment contains an epoxy dicyclopentenyl (EDCP) monomer unit, effectively reducing the degree of heat shrinkage when the coating layer of the colored resin composition is subjected to a high-temperature process, and Deformation caused by the high-temperature process of the coating layer can be suppressed, and the material coating layer to be continuously formed can still adhere well to the coating layer of the colored resin composition even through the high-temperature process. Therefore, the heat resistance and stability of the entire structure are improved.

In the embodiment of the present disclosure, the resin of the colored resin composition contains an epoxy dicyclopentenyl (EDCP) monomer unit, so that the degree of heat shrinkage when the coating layer of the colored resin composition is subjected to a high-temperature process is effectively reduced. In addition, deformation caused by the high-temperature process of the coating layer of the colored resin composition can be suppressed, and even if the subsequent material coating layer passes through the high-temperature process, it can still adhere well to the coating layer of the colored resin composition. Therefore, the heat resistance and stability of the entire structure are improved. Hereinafter, various embodiments are presented and detailed descriptions are given, but these embodiments are only examples, and the present disclosure does not limit or reduce the scope for pursuing protection, and the present disclosure provides other features and components. , Method and parameter can also be used. The presentation of the embodiments has been made to illustrate the technical features of the present disclosure, and does not limit the claims of the present disclosure. Those skilled in the art can make equivalent changes and changes without departing from the spirit and scope of the present disclosure, based on the description of the following specification.

Some embodiments of the present disclosure relate to colored resin compositions. Such a colored resin composition contains a coloring agent (A), a resin (B), a photopolymerizable monomer (C), a photoinitiator (D), and a solvent (E). Resin (B) contains an epoxy dicyclopentenyl monomer unit and a silane monomer unit.

Here, the terms of components such as colorant (A), resin (B), photopolymerizable monomer (C), photopolymerization initiator (D), and solvent (E) are each independently a single type or multiple types of colorants ( A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) and a solvent (E) may include the case.

In the manufacturing process of the display device, after the coating and developing process of the color resist is completed, it is necessary to continuously apply a plurality of different material layers on the color resist, and several high-temperature processes (for example, 220° C. to 250[deg.] C.) to dry these material layers and at the same time adhere to the color resist. However, the color resist tends to cause volume contraction during the high-temperature baking process, and there is a high possibility that a poor adhesion between the material layer and the color resist is caused by this.

According to an embodiment of the present disclosure, the resin (B) contains the resin (B-1), the resin (B-1) contains the epoxy dicyclopentenyl (EDCP) monomer unit, and the colored resin composition The degree of heat shrinkage when performing the high-temperature process of the coating layer is effectively reduced, so that deformation caused by the high-temperature process of the coating layer of the colored resin composition can be suppressed, and thus the subsequent material coating layer is still colored even after the high-temperature process. It can be made to adhere well to the coating layer of the resin composition. This increases the heat resistance and stability of the entire structure.

Specifically, according to an embodiment of the present disclosure, the epoxydicyclopentenyl monomer unit has a three-dimensional three-dimensional structure, increases the strength of the crosslinked polymer network of the resin, thereby making the structure of the colored resin composition more robust. Therefore, the coating layer is relatively difficult to decompose or shrink even when subjected to heat, so that the heat resistance stability of the coating layer of the colored resin composition can be improved.

Further, according to an embodiment of the present disclosure, the resin (B) further comprises a resin (B-2). Resin (B-2) contains a silane monomer unit, and the silicone atom in the silane monomer unit has a size larger than that of the carbon atom in the polymer structure, and forms a longer chain length. For this reason, combining the silane monomer unit with the epoxy dicyclopentenyl monomer unit in the resin (B) is more helpful in reducing the volume shrinkage when subjected to heat, and is useful in improving the heat resistance and stability of the entire structure. Do.

In some embodiments, the colorant (A) may include pigments and/or dyes. According to some embodiments, the pigment as the colorant (A) is not particularly limited, and a known pigment may be used, for example, a compound classified as a pigment in the color index (published by The Society of Dyers and Colorists). Can be mentioned. According to some embodiments, the dye as the colorant (A) is not particularly limited, and may be appropriately selected according to the spectrum of a desired color filter. In some embodiments, the dye may preferably be a xanthone dye.

In some embodiments, the colorant (A) may occupy 3% by weight or more of the colored resin composition, for example. In some embodiments, the colorant (A) may account for 4% to 10% by weight of the colored resin composition, for example. In some embodiments, the dye may account for about 1 to 100% by weight of the colorant (A), preferably about 5 to 95% by weight.

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

In formula (I), R ⁴¹ to R ⁴⁴ are each independently 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 7 to 30 carbon atoms which may have a substituent. Represents an aralkyl group of, and the aromatic hydrocarbon group and the substituent that the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , and hydrogen atoms contained in the saturated hydrocarbon group are , May be substituted with a substituted or unsubstituted amino group or a halogen atom. When the saturated hydrocarbon group has 2 to 20 carbon atoms, -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, adjacent -CH ₂ -is not simultaneously substituted with -O-, and -CH ₂ -at the terminal is not substituted with -O- or -CO-. R ⁴¹ and R ⁴² may form a bond, and may form a ring together with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to each other, and may form a ring with the nitrogen atom to which they are bonded.

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, the alkyl group -CH ₂ -constituting a may be substituted with at least one of -O- and -CO-, and even if R ⁴⁸ and R ⁵² are bonded to each other to form -NH-, -S- or -SO _2- do. However, in the alkyl group, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O- or -CO-.

Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms, and the aromatic heterocycle has a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent The substituent which may be present and the aromatic hydrocarbon group may have includes -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

M ^r+ is a hydrogen ion, an r-valent metal ion, or a substituted or unsubstituted ammonium ion; k is the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f of R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ ; r represents an integer of 1 or more. R ^f represents a C1-C12 fluoroalkyl group. However, 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 heterocycle represented by ring T ¹ may be a monocyclic ring or a condensed ring. The aromatic heterocycle represented by the ring T ¹ has 3 to 10 carbon atoms, preferably 3 to 8. In addition, the aromatic heterocycle is preferably a 5 to 10 membered ring, and more preferably a 5 to 9 membered ring. Examples of the monocyclic aromatic heterocycle include a 5-membered ring containing a nitrogen atom such as a pyrrole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; 5-membered rings that do not contain nitrogen atoms, such as a furan ring and a thiophene ring; And 6-membered rings containing nitrogen atoms, such as a pyridine ring and a pyrimidine ring. Examples of the aromatic heterocycle of the condensed ring include condensed rings containing nitrogen atoms such as an indole ring, a benzoimidazole ring, a benzothiazole ring, and a quinoline ring; Condensed rings which do not contain a nitrogen atom, such as a benzofuran ring, etc. are mentioned.

The aromatic heterocycle of ring T ¹ may have a substituent, and examples of the substituent include a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted or unsubstituted amino group, or a carbon number that may have a substituent. 6 to 20 aromatic hydrocarbon groups, and the like, preferably a C 1 to C 20 saturated hydrocarbon group, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Ring T ¹ preferably has an amino group which may have a substituent, and examples of the substituent that the amino group may have include a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and a substituent Aralkyl groups having 7 to 30 carbon atoms which may have are preferable.

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

In some embodiments, ring T ¹ can be a ring represented by Formula (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 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 7 to 30 carbon atoms which may have a substituent When an aralkyl group is represented and the number of carbon atoms of the saturated hydrocarbon group is 2 to 20, -CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O- or -CO-. R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a ring together with the nitrogen atom bonded to the R ⁴⁵ and R ⁴⁶ . * Represents the bonding position with a carbo cation in formula (I).

In some embodiments, ring T ¹ may be a ring represented by the following formula (t2):

In formula (t2), ring T ³ represents an aromatic heterocycle 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 hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f ; R ⁵⁹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent; k2 represents 0 or 1; * Represents the bonding end of the carbocation in the formula (I).

In some embodiments, ring T ¹ can be a ring represented by formula (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 has the same meaning as R ⁵ in the above formula (t2). * Represents the bonded end of the carbo cation in the formula (I).

In R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ , a saturated hydrocarbon group having 1 to 20 carbon atoms and a saturated hydrocarbon group having 1 to 20 carbon atoms which may be included in an amino group capable of substituting the ring T ¹ are linear , Branched chain shape or ring shape may be sufficient. As a linear or branched saturated hydrocarbon group, a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, eicosyl group, etc. A straight-chain alkyl group of; And branched-chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group. The number of carbon atoms in the saturated hydrocarbon group may be 1 to 10, more preferably 1 to 8, and still more preferably 1 to 6.

The cyclic saturated hydrocarbon group for R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ , and the cyclic saturated hydrocarbon group which may be contained in the amino group that may be contained in the ring T ¹ may be monocyclic or polycyclic. It may be. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an alicyclic saturated hydrocarbon group such as an adamantane group. The number of carbon atoms in the cyclic saturated hydrocarbon group may be 3 to 10, preferably 6 to 10.

Among R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ , the saturated hydrocarbon group and the saturated hydrocarbon group which may be included in the amino group which ring T ¹ may have may have a substituted or unsubstituted amino group or a halogen atom as a substituent. have. As a substituted amino group, an alkylamino group, such as a dimethylamino group and a diethylamino group, is mentioned, for example. Further, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. 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 a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group.

The alkyl group having 1 to 8 carbon atoms for R ⁴⁷ to R ⁵⁴ may be a saturated hydrocarbon group having 1 to 8 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified by the saturated hydrocarbon group for R ⁴¹ .

Further, the alkyl group having 1 to 10 carbon atoms for R ⁵⁷ may be a saturated hydrocarbon group having 1 to 10 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified by the saturated hydrocarbon group for R ⁴¹ .

When the saturated hydrocarbon group for R ⁴¹ to R ⁴⁶ has 2 to 20 carbon atoms, -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, adjacent -CH ₂ -is not simultaneously substituted with -O-, and -CH ₂ -at the terminal is not substituted with -O- or -CO-. In this case, as the saturated hydrocarbon group, a linear or branched saturated hydrocarbon group (i.e., a linear or branched alkyl group) is preferable, and a linear saturated hydrocarbon group (i.e., a linear alkyl group) is more preferable. Do. 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 -O- or -CO- and -O- or -CO- The number of carbon atoms in between may be 1 or more, or 1 to 5, and preferably 2 to 3.

In addition, the aromatic hydrocarbon group which may have a substituent for R ⁴¹ to R ⁴⁶ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ , and the aromatic hydrocarbon group which may be contained in the substituted amino group which ring T ¹ may have (corresponding aromatic hydrocarbon The group may have a substituent) has preferably 6 to 20 carbon atoms, or 6 to 15 or 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl 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 xylyl group are preferable. . Further, 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, oxo atom and bromine atom; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; Hydroxy group; Sulfamoyl group; Alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl groups; Alkoxycarbonyl groups having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; -SO ₃ ^-; -SO ₂ -N ^-- SO ₂ -R ^f etc. are mentioned. In some embodiments, the aromatic hydrocarbon group comprises -SO ₃ ^- and/or -SO ₂ -N ^-- SO ₂ -R ^f as a substituent, and -SO ₃ ^- and/or -SO ₂ -N ^-- SO ₂ -R ^f and the aromatic hydrocarbon ring of the aromatic hydrocarbon group are directly bonded, that is, -SO ₃ ^- and/or -SO ₂ -N ^-- SO ₂ -R ^f replaces the hydrogen atom bonded to the aromatic hydrocarbon ring .

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

As the aralkyl group which may have a substituent for R ⁴¹ to R ⁴⁶ and R ⁵⁹ , and the aralkyl group which may be contained in the substituted amino group which ring T ¹ may have (the aralkyl group may have a substituent), methylene A group formed by bonding an alkylene group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a group, an ethylene group, and a trimethylene group to the aromatic hydrocarbon group, and the like. The number of carbon atoms of the aralkyl group may be 7 to 30, or 7 to 20, or 7 to 17 carbon atoms.

A ring formed with the nitrogen atom to which R ⁴¹ and R ⁴² are bonded to each other, a ring formed with the nitrogen atom to which R ⁴³ and R ⁴⁴ are bonded, and R ⁴⁵ and R ⁴⁶ are bonded to each other Examples of the ring formed with the nitrogen atom include a non-aromatic 4-membered to 7-membered ring containing nitrogen such as a pyrrolidine ring, a morpholine ring, and a piperidine ring, and preferably a pyrrolidine ring or piperi Examples of heteroatoms such as a din ring include 4- to 7-membered rings having only one nitrogen atom.

As R ⁵⁸ , 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 is preferable.

As R ⁴¹ to R ⁴⁴ , R ⁵⁶ , and R ⁵⁸ to R ⁶⁰ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable, and each independently a saturated hydrocarbon group having 1 to 8 carbon atoms or the following formula It is more preferable that the group represented by R ⁵⁶ and R ⁵⁸ to R ⁶⁰ are more preferably a group represented by the following formula. In the following formula, * represents the bonded end of the nitrogen atom.

R ⁴⁵ to R ⁴⁶ are preferably, each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which -CH ₂ -in the alkyl group having 2 to 20 carbon atoms is substituted with at least one of -O- and -CO- Or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; Alternatively, R ⁴⁵ and R ⁴⁶ combine to form a ring together with the nitrogen atom to which they are bound. In some embodiments, R ⁴⁵ to R ⁴⁶ may each independently be a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R ⁴⁵ and R ⁴⁶ are bonded to each other to form nitrogen as a heteroatom. It forms a 4- to 7-membered ring having only one atom. In the following formula, * represents the bonded end of the nitrogen atom.

In addition, as the alkyl group having 1 to 8 carbon atoms for R ⁴⁷ to R ⁵⁴ , a saturated hydrocarbon group having 1 to 8 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified for the saturated hydrocarbon group for R ⁴¹ Can be lifted. Further, in the alkyl group having 2 to 8 carbon atoms in R ⁴⁷ to R ⁵⁴ , -CH ₂ -is substituted with at least one of -O- and -CO- (however, in the alkyl group, adjacent -CH ₂ -Is not substituted with -O- at the same time, and -CH ₂ -at the terminal is not substituted with -O- or -CO-), for example, 2 to 2 carbon atoms as described above for R ⁴¹ to R ⁴⁶ Among the groups formed by substituting at least one of -O- and -CO- for -CH ₂ -in the 20 alkyl group, a group having 8 or less carbon atoms is exemplified.

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, and more preferably each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

R ⁵⁷ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ⁶¹ is preferably a hydrogen atom.

Examples of 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; Transition metal ions such as titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions and copper ions; Typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and bismuth ions, and the like. r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. Further, examples of the substituted or unsubstituted ammonium ion represented by M ^r+ include quaternary ammonium ions such as tetraalkyl ammonium ions.

As M ^r+ , hydrogen ions or r-valent metal ions may be used, alkaline earth metal ions, typical metal ions, and the like are more preferable, alkaline earth metal ions and zinc ions are still more preferable, and alkaline earth metal ions are still more preferable.

The number of M ^r+ in formula (I) is the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f of R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ It is one less than the sum (k). For this reason, the compound (I) becomes a compound having a valence of 0, that is, an electrically neutral compound.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms in R ^f include monofluoromethyl group, difluoromethyl group, perfluoromethyl group, monofluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, Perfluoroethyl group, monofluoropropyl group, difluoropropyl group, trifluoropropyl group, tetrafluoropropyl group, pentafluoropropyl group, hexafluoropropyl group, perfluoropropyl group, monofluoro Butyl group, difluorobutyl group, trifluorobutyl group, tetrafluorobutyl group, pentafluorobutyl group, hexafluorobutyl group, heptafluorobutyl group, octafluorobutyl group, perfluorobutyl group And the like. Among these, as the fluoroalkyl group represented by R ^f , a perfluoroalkyl group is preferable. Further, the number of carbon atoms in the fluoroalkyl group represented by R ^f is preferably 1 to 10, more preferably 1 to 5, and still more 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 number of -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f of R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ is 1 or more, preferably It is 1 to 7, more preferably 2 to 7, further preferably 2 to 4, and more preferably 2 or 3.

From -SO ₂ -R ^f is desirable to meet at least one or more conditions selected from (a) to (d) below, and (a) and (b) ^- -SO ₃ ^- or -SO ₂ -N It is more preferable to satisfy at least one or more conditions selected.

(a) contained in at least one of R ⁴⁷ to R ⁵⁴

(b) bonded to any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent represented by R ⁴¹ to R ⁴⁴

(c) bonded to any of the aralkyl groups having 7 to 30 carbon atoms which may have a substituent represented by R ⁴¹ to R ⁴⁴

(d) bonded to any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms replacing the hydrogen atom of the aromatic heterocycle represented by T ¹

However, -SO ₃ ^- or When -SO ₂ -N ^-- SO ₂ -R ^f is bonded to an aromatic hydrocarbon group or an aralkyl group, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is an aromatic hydrocarbon group or an aralkyl group It is preferably directly bonded to the aromatic hydrocarbon ring of. That is, it is preferable that -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f replaces the hydrogen atom bonded to the aromatic hydrocarbon ring.

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

When a plurality of -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is included in compound (I), a plurality of -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f are the same aromatic It may be bonded to a hydrocarbon ring, but it is preferable to bond to another aromatic hydrocarbon ring.

It is preferable that compound (I) does not have an olefinic unsaturated bond.

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

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

In formula (IC), R ¹ to R ⁴ are each independently 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 7 to 30 carbon atoms which may have a substituent. Represents an aralkyl group of, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and -CH ₂ -contained in the saturated hydrocarbon group is You may be substituted with at least 1 of -O- and -CO-. R ¹ and R ² may be bonded to each other, and may form a ring with the nitrogen atom bonded to them, or R ³ and R ⁴ may be bonded to each other to form a ring with the nitrogen atom bonded to them. R ⁷ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and -CH ₂ -constituting the alkyl group is among -O- and -CO- At least one may be substituted. R ⁸ and R ¹² may be bonded to each other to form -NH-, -S- or -SO ₂ -. Ring T ¹⁰ represents an aromatic heterocycle having 3 to 10 carbon atoms, and the aromatic heterocycle may have 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. M ¹ is Cl ^-, phosphate ion, perchlorate ion, BF ₄ ^- or PF ₆ ^- shows a.

When compound (I) has a -SO ₃ ^- group and does not have -SO ₂ -N ^-- SO ₂ -R ^f (hereinafter sometimes referred to as "compound (A1-a)"), the compound ( A1-a) and the compound represented by formula (IB) may react.

In Formula (IB), R ^f has the same meaning as R ^f described above.

In addition, when compound (I) is a compound in which M ^r+ in formula (I) is a hydrogen ion (hereinafter, it may be referred to as compound (IA-2)), compound (IA-2) and r-valent metal ion A halide (preferably chloride), acetate, phosphate, sulfate, silicate, or cyanide may be reacted.

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

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

In some embodiments, the second colorant is a compound having a structure represented by 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, a phenyl group which may have a substituent, or -R ²⁰ -Si(R ¹⁹ ) ₃ .

-R ²⁰ -Si (R ¹⁹⁾ 3 of the _three R ¹⁹ each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 in which p is 1 to 100; R ²⁰ is an alkylene group having 1 to 10 carbon atoms, and -CH ₂ -in the alkylene group constituting R ²⁰ is -O-, -CO-, -NR ²¹ -, -OCO-, -COO-, -OCONH- , -CONH- or -NHCO- may be substituted.

The hydrogen atom of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and -CH ₂ -in this saturated hydrocarbon group is -O-, -CO-, -NR ²¹ -, -OCO- , -COO-, -OCONH-, -CONH-, or -NHCO- may be substituted. However, in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, adjacent -CH ₂ -is not substituted at the same time, and -CH ₂ -at the terminal is not substituted.

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 selected from _{^{-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 a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms The hydrogen atom of may be substituted with a halogen atom.

Z ⁺ may be [N(R ²⁶ ) ₄ ] ⁺ , Na ⁺ or K ⁺ ; Each of the four R ²⁶ is 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;

n is an integer from 0 to 4;

a is 0 or 1.

In some embodiments, when -SO ₃ ^- is present in Formula (II), the number is 1.

The substituent of the phenyl group which may have a substituent at the R ¹¹ to R ^14, 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 . Of these, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z ⁺ and a -SO ₂ NR ²⁴ R ²⁵ are preferred. Examples of _{^{Z +, -SO 3 - - -SO}} 3 in this case, N (R ²¹⁾ ₄ ⁺ being preferred.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ¹¹ to R ¹⁴ and R ²⁰ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, no Linear alkyl groups such as a nil group and a decyl group; Branched-chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; And alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of R ²⁰ in -R ²⁰ -Si(R ¹⁹ ) ₃ include an alkylene group such as a methylene group, an ethylene group, and a trimethylene group. Examples of the C1-C4 alkyl group for R ¹⁹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms for R ¹⁹ include a methoxy group, an ethoxy group, a propoxy group, and a t-butoxy group.

As -OR ²⁴ , a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, an icosyloxy group, etc. are mentioned.

Examples of -CO ₂ R ²⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of -SO ₃ R ²⁵ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

-SO ₂ NR ²² R ^{23 is a} sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfa Moyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1 ,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N,N-2 substituted sulfa such as N-(3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, and N-(1,3-dimethylbutyl)sulfamoyl group Gathering, etc. are mentioned.

In some embodiments, equation (II) is electrically neutral, ie, a is zero. In some embodiments, formula (II) has a monovalent static charge, in which case formula (II) can combine commonly used monovalent anions, such as halogen ions.

In some embodiments, Formula (II) may have a structure represented by the following (A2-1) to (A2-10):

The second colorant is a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Chugaikasei Co., Ltd., and "Chugai Aminol Fast Pink RH/C" manufactured by Taoka Chemical Co., Ltd. Rhodamin 6G") can be used as a starting material and synthesized by referring to Japanese Laid-Open Patent No. 2010-32999.

In some embodiments, the second colorant used likewise comprises silicone (e.g., in formula (II), wherein at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ is R ^20- Si(R ¹⁹ ) ₃ ), compared to other types of second colorants, the compatibility with the silane monomer units (the structure of which will be described later) of the present invention likewise containing silicone may be better.

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

The dyes other than the first colorant and the second colorant are not particularly limited, and known dyes may be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes and the like. As dyes, for example, compounds classified as having colors other than pigments in the color index (published by The Society of Dyers and Colorists), or dye notes (Shikisensha) Known dyes described in are mentioned. In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, a Cridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. The pigment is also not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments in the color index (published by The Society of Dyers and Colorists). In some embodiments, the colorant in the colored resin composition (e.g., when the colored resin composition has only the first colorant, it is calculated as the first colorant; when the first colorant and the colorant other than the first colorant are included, (Calculated with all colorants), assuming that the solid component in the composition is 100 parts by weight, 1 to 40 parts by weight is preferable, and it is more preferably 3 to 35 parts by weight. When the content of the colorant is within the above range, the color density when produced by the color filter is sufficient, and a resin and a polymerizable compound can be contained in a desired amount in the composition, so that a pattern having sufficient mechanical strength can be formed. The "solid component" in the present invention refers to the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid components and the content of each component relative thereto can be measured by suitable analytical means such as liquid chromatography or gas chromatography.

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

Depending on actual demand, a dispersant may be contained in the solid component so that the colorant is uniformly dispersed in the solution. Examples of the dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamine surfactants, and acrylic surfactants. These dispersants may be used alone, or two or more types may be used in combination. As a pigment dispersant, as a brand name, KP (made by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (made by Kyoeisha Chemical Co., Ltd.), and Solsperse ( Registered trademark) (product of GENEKA CORPORATION), EFKA (product of CIBA), AJISPER (registered trademark) (product of Ajinomoto Fine Techno), Disperbyk (registered trademark) (BYK) -Chemie's product), etc. are mentioned.

In some embodiments, the resin (B) may be an alkali-soluble resin, such as, but not limited to, a resin containing a structural unit having a methacrylic acid derivative.

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

According to some embodiments of the present disclosure, when the content of the epoxy dicyclopentenyl monomer unit is lower than the lower limit, the effect of strengthening the crosslinked polymer network of the resin may be lowered, and the epoxy dicyclopentenyl monomer When the content of the unit is higher than the above upper limit, an exclusion effect occurs with respect to the content of other necessary components, and thereby there is a possibility that the crosslinking strength of the polymer network is lowered. Therefore, according to some embodiments of the present disclosure, when the content of the epoxy dicyclopentenyl monomer unit is in the above range, the most effective can be exhibited with respect to the improvement of heat resistance and stability of the entire structure.

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

According to some embodiments of the present disclosure, when the ratio of the number of epoxydicyclopentenyl monomer units and the number of silane monomer units is in the above range, the silicon atom or the silane functional group of the silane monomer unit is not excessively increased. , It is possible to achieve an effect of not adversely affecting the predetermined chemical and physical properties of the colored resin composition, maintaining predetermined properties of the colored resin composition, and contributing to improving the crosslinking strength of the polymer network.

In some embodiments, with respect to 100 parts by weight of the epoxydicyclopentenyl monomer unit, the silane monomer unit is 2 parts by weight to 8 parts by weight, preferably 3 parts by weight to 7 parts by weight, more preferably 3.5 parts by weight. It is to 6 parts by weight.

In some embodiments, the epoxydicyclopentenyl monomer unit of the resin (B-1) is a first monomer unit having a structure represented by the following formula (1) and a second monomer unit having a structure represented by the following formula (2). It may contain at least one of the monomer units:

[Formula 1]

In the formula, 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 with a hydroxy group, and X1 is a single bond, -R3-, -R3-O-, -R3 Represents -S- or -R3-NH-, of which R3 represents an alkylene group having 1 to 6 carbon atoms, and n is a positive integer;

[Formula 2]

In the formula, R2 represents 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 with a hydroxy group, and X2 is a single bond, -R3-, -R3-O-, -R3 -S- or -R3-NH- is represented, and m is a positive integer.

In some embodiments, the epoxydicyclopentenyl monomer unit of the resin (B-1) is a monomer unit having a structure represented by the following Formula 1A, and a second monomer unit having a structure represented by the following Formula 2A. May contain:

[Formula 1A]

[Formula 2A]

.

.

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

In some embodiments, the resin (B-1) is a monomer having a structural unit derived from the monomer (m2-1), a cyclic ether structure having 2 to 4 carbon atoms, and an olefinic unsaturated bond (hereinafter, "monomer ( m2-2) may be a copolymer having a structural unit derived from ""). The copolymer may contain other structural units. As another 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 an olefinic unsaturated bond And structural units having Even if only 1 type of said structural unit is contained in a copolymer, 2 or more types may be contained further.

As the monomer (m2-1), for example, (1) unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic 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-tetra Unsaturated dicarboxylic acids such as hydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; (3) Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hepto-2-ene, 5,6-dicarboxybicyclo[2.2.1]hepto-2- N, 5-carboxy-5-methylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbi Bicyclounsaturated compounds containing a carboxy group such as cyclo[2.2.1]hepto-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hepto-2-ene; (4) Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetra Unsaturated dicarboxylic acid anhydrides such as hydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride; (5) Unsaturated mono [(meth)acrylic acid of divalent or higher polyvalent carboxylic acids such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] Monooxyalkyl] esters; Or (6) unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid, and the like.

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

The monomer (m2-2) may be, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, an oxirane ring, an oxetane ring, or a tetrahydrofuran ring) and an olefinic unsaturated bond. It is preferable that the monomer (m2-2) is a monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group.

As the monomer (m2-2), for example, an epoxy ethyl group and a monomer having an olefinically unsaturated bond (hereinafter, sometimes referred to as "monomer (m2-2-1)"), an oxetanyl group and an olefinic unsaturated bond A monomer (hereinafter sometimes referred to as "monomer (m2-2-2)"), or a monomer having a tetrahydrofuryl group and an olefinic unsaturated bond (hereinafter referred to as "monomer (m2-2-3)" in some cases ), etc.

As the monomer (m2-2-1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (m2-2-1a)") , A monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, it may be referred to as "monomer (m2-2-1b)").

As the monomer (m2-2-1a), a monomer having a glycidyl group and an olefinically unsaturated bond is preferable. As the monomer (m2-2-1a), for example, glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl Vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α- Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyl Oxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) Styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) ) Styrene, 2,4,6-tris (glycidyloxymethyl) styrene, etc. are mentioned.

As the monomer (m2-2-1b), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE (registered trademark) 2000; Daicel Corporation ( Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth) ) Acrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel), a compound represented by the following formula (III), and a compound represented by the formula (IV).

In formulas (III) and (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 with a hydroxy 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 end of the bond with O.

Examples of the compound represented by formula (III) include compounds represented by any of the following formulas (III-1) to (III-15). Among them, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9), or formula (III-11) to formula (III-15 A compound represented by) is preferred.

Examples of the compound represented by formula (IV) include compounds represented by any of the following formulas (IV-1) to (IV-15). Among these, formula (IV-1), formula (IV-3), formula (IV-5), formula (IV-7), formula (IV-9), or formula (IV-11) to formula (IV-15 ) Is preferably a compound represented by a formula (IV-1), a formula (IV-7), a formula (IV-9) or a formula (IV-15).

The compound represented by formula (III) and the compound represented by formula (IV) may be used independently, respectively, or two or more types may be used in combination. When a compound represented by formula (III) and a compound represented by formula (IV) are used in combination, the content ratio [compound represented by formula (III): compound represented by formula (IV)] is a molar ratio of 5 :95 to 95:5 are preferable, and it is more preferable that it is 20:80 to 80:20.

As a monomer (m2-3), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) Acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth) Acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in the technical field, as a common name, "dicyclopentanyl (meth) Acrylate". In addition, it may also be referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (corresponding technology In the field, it is referred to as "dicyclopentenyl (meth)acrylate" as a common name), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate , (Meth)acrylic acid esters such as allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid; bicyclo[2.2.1]hepto-2-ene, 5-methylbicyclo[2.2.1]hepto-2-ene, 5- Ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxybicyclo[2.2.1]hepto-2-ene, 5-hydroxymethylbicyclo[2.2.1]hepto-2-ene, 5 -(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2-ene, 5-methoxybicyclo[2.2.1]hepto-2-ene, 5-ethoxybicyclo[2.2.1] Hepto-2-ene, 5,6-dihydroxybicyclo[2.2.1]hepto-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hepto-2-ene, 5 ,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2-ene, 5,6-dimethoxybicyclo[2.2.1]hepto-2-ene, 5,6-di Ethoxybicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1 ]Hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hepto-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hepto-2-ene, 5,6-bis(tert-butoxycarbo Bicyclounsaturated compounds such as nil)bicyclo[2.2.1]hepto-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;

Styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic Amide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

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

It is preferable that the structural unit which has an olefinic unsaturated bond is a structural unit which has a (meth)acryloyl group. The resin (B-1) having such a structural unit is capable of reacting a polymer containing a structural unit derived from a monomer (m2-1) and a structural unit derived from the monomer (m2-2) with a group of the structural unit. It can be obtained by reacting with a group and a monomer having an olefinic unsaturated bond.

As a structural unit having an olefinic unsaturated bond, for example, a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, and 2-hydroxyethyl (meth)acrylate to a maleic anhydride unit And a structural unit obtained by adding a carboxylic acid anhydride to a structural unit having a hydroxy group, a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, and the like. .

The polymer containing the structural unit derived from the monomer (m2-1) can be produced, for example, by polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator and solvent are not particularly limited, and materials generally used in the relevant field may be used. As a polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl Peroxide, etc.). As a solvent, what is necessary is just to dissolve each monomer of resin (B-1), For example, the solvent etc. which become the colored resin composition of this invention mentioned later are mentioned.

In the production of a polymer containing a structural unit derived from the monomer (m2-1), as the monomer, a carboxylic anhydride having an olefinic unsaturated bond can be used. Examples of carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride.

As resin (B-1), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxycyclohexylcyclo[5.2.1.0 ^2.6 ]decylacrylate/(meth)acrylic acid Resins such as copolymers; Glycidyl(meth)acrylate/benzyl(meth)acrylate/(meth)acrylic acid copolymer, glycidyl(meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxycitracyclo[ 5.2.1.0 ^2.6 ]decylacrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, Benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, and Japanese Laid-Open Patent No. Hei 9-106071, Japanese Laid-Open Patent No. 2004-29518 and Japanese Laid-open Resins described in Patent No. 2004-361455, etc. are mentioned.

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

In some embodiments, when the resin (B-1) and the resin (B-2) described later are used simultaneously, the weight ratio of the solid component of the resin (B-1) is the solid component of the resin (B-2). It is smaller than this weight ratio. For this reason, even under a high exposure dose, a good degree of analysis can be maintained for the colored resin composition. In some embodiments, the total weight of resin (B-1) may be 50% or less, or 45% or less of the total weight of resin (B-2).

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 The total weight of may be 20 to 60 parts by weight, or 30 to 55 parts by weight.

In some embodiments, the silane monomer unit of resin (B-2) may have a structure represented by the following formula (3):

In the formula, R4 represents a hydrogen atom or a methyl group;

Each of R5 to R7 independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Provided that at least one of R5 to R7 is an alkoxy group having 1 to 6 carbon atoms;

p is a positive integer, and q is an integer from 1 to 10.

By using a silicone resin having a silane monomer unit represented by Formula 3 in combination with a first colorant, a fine hole pattern having good resolution can be formed on the formed colored resin composition film layer even when the exposure amount is high. .

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

Examples of the alkyl group having 1 to 6 carbon atoms in R5 to R7 include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, isopropyloxy group, isobutoxy group, isopentyloxy group, Neopentyloxy group is mentioned.

Each of R5 to R7 may be independently a methoxy group, an ethoxy group or a propoxy group, and more preferably a methoxy group or an ethoxy group. q may be an integer of 1 to 6, or may be an integer of 1 to 3.

In some embodiments, the silane monomer unit may have a structure represented by Formula 3A below:

[Chemical Formula 3A]

.

.

In some embodiments, the silane monomer unit may have a structure represented by the following Formula 3B:

[Chemical Formula 3B]

In some embodiments, the resin (B-2) containing the silane monomer unit is a constituent unit (b1-2) derived from a polymerizable unsaturated compound having an acidic group (hereinafter referred to as “constituent unit (b1-2)” ) And another structural unit (b1-3) (hereinafter referred to as "constituent unit (b1-3)") may further contain a copolymer. In the present invention, the other structural unit (b1-3) represents a structural unit different from the silane monomer unit and the structural unit (b1-2). In (B-2), only 1 type or 2 or more types of a silane monomer unit, a structural unit (b1-2), and a structural unit (b1-3) may be contained.

Examples of the acidic group of the structural unit (b1-2) include a carboxy group, a phosphoric acid group (-OP(=O)(OH) ² ), and a sulfo group (-S(=O) ₂ OH). Among these, a carboxy group is preferable.

From the viewpoint of solvent resistance, when the total of all structural units in the copolymer is 100 mol%, the content of the silane monomer units can be 1 to 50 mol%, 5 to 40 mol%, or 10 to 30 mol% It is more preferable if it is %.

When the total of all the structural units in the copolymer is 100 mol%, the content of the structural unit (b1-2) can be 10 to 50 mol% from the viewpoint of developability, and 15 to 45 mol%, or 20 It is more preferable that it is-40 mol%.

In order to give the formed colored resin composition more excellent developability, the weight average molecular weight (Mw) of the resin (B-2) may be 1,000 to 50,000, or 2,000 to 40,000. The weight average molecular weight (Mw) may be calculated in terms of polystyrene using gel permeation chromatography (GPC).

In some embodiments, the silane group equivalent in the resin (B-2) is preferably 400 to 4,000, more preferably 500 to 3,000, from the viewpoint of thermal decomposition resistance, heat yellowing resistance, and solvent resistance. When the silane group equivalent of the resin (B-2) is 400 or more, the thermal decomposition resistance and heat yellowing resistance of the colored pattern or colored coating film can be improved. The silane group equivalent of resin (B-2) is the following formula:

Silane group equivalent = weight average molecular weight of resin (B-2)/1 average number of silane groups per molecule

It is a value calculated from

The silane group equivalent can be calculated from the injected amount of the monomer used in the production of the resin (B-2).

In some embodiments, when the resin (B-2) is a copolymer containing the structural unit (b1-2), from the viewpoint of developability, the acid value of the resin (B-2) is preferably 20 to 300 mg It can be KOH/g, and it is more preferable that it is 30-200 mgKOH/g. The acid value of the resin (B-2) is a value measured using a mixture indicator of bromothymol blue and phenol red according to JIS K6901 5.3, and the amount of potassium hydroxide required to neutralize 1 g of the resin (B-2) ( Mg), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

In some embodiments, after alkali development, in order to form a good pattern without defects or peeling, the polymerizable compound in the resin (B-2) and the colored resin composition (i.e., photopolymerizable monomer (C), described in more detail later) Can be done in a specific ratio. In some embodiments, when 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.

In some embodiments, the resin (B-2), in the presence of a solvent for polymerization, a compound (m1-1) represented by the following formula (2b), or a compound (m1-1) and other compounds Using a monomer mixture containing, it can be obtained by performing copolymerization by radical polymerization or other suitable method:

Symbols in formula (2b) have the same meaning as described above.

In some embodiments, the resin (B-2) is prepared by dissolving compound (m1-1) and other compounds as necessary in a polymerization solvent to prepare a solution, and then adding a polymerization initiator to the solution, 50 to It can be obtained by reacting at 130°C for 1 to 20 hours.

In some embodiments, the resin (B-2) containing the silane monomer unit, the structural unit (b1-2), and the structural unit (b1-3), in the presence of a polymerization solvent, compound (m1-1), A monomer mixture consisting of a polymerizable unsaturated compound having an acidic group (hereinafter referred to as "Compound (m1-2)") and another polymerizable unsaturated compound (hereinafter referred to as "Compound (m1-3)") is a known radical polymerization It is obtained by copolymerizing by a method. Here, the other polymerizable unsaturated compound (m1-3) means a polymerizable unsaturated compound different from the compound (m1-1) and the compound (m1-2). In addition, the silane monomer unit is derived from compound (m1-1), the structural unit (b1-2) is derived from compound (m1-2), and the structural unit (b1-3) is derived from compound (m1-3) do.

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

As the compound (m1-1), for example, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acrylic Royloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxy And propyl triethoxysilane. Among these, 3-(meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyltriethoxysilane are preferable from the viewpoint of availability and reactivity. In the present invention, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid. Other similar descriptions have the same meaning.

Examples of the acidic group of the compound (m1-2) include a carboxy group, a phosphoric acid group (-OP(=O)(OH) ² ), and a sulfo group (-S(=O) ₂ OH). Among these, a carboxy group is preferable.

Specific examples of the compound (m1-2) are, for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, and 2-acryloyloxyethylphthalic acid. , 2-(meth)acryloyloxyethylhexahydrophthalic acid, and 2-(meth)acryloyloxyethyl acid phosphate. Among these, (meth)acrylic acid is preferable from the viewpoint of availability and reactivity.

Examples of the compound (m1-3) include (1) dienes such as butadiene; (2) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (Meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylic Rate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate , Methylcyclohexyl (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, 1,1,1-trifluoroethyl (meth) )Acrylate, perfluoroethyl (meth) acrylate, perfluoro-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) Acrylate, 3-(N,N-dimethylamino)propyl(meth)acrylate, glycerylol mono(meth)acrylate, butanetriolmono(meth)acrylate, pentanetriolmono(meth)acrylate, Dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylic Rate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetane-3 -Yl)methyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2 -Isocyanato-1-methylethyl (meth)acrylate, 2 -Isocyanato-1,1-dimethyl ethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, isocyanato group of ethylenically unsaturated compounds having the above isocyanato group A compound having a blocked isocyanato group obtained by blocking with a blocking agent, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N-tert- Methyl (meth)acrylates such as butylaminoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, and hexamethylpiperidyl (meth)acrylate; (3) (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N (Meth)acrylic acid amides, such as N-diisopropylamide, (meth)acrylate anthracenylamide, N-isopropyl (meth)acrylamide, (meth)acrylmorpholine, and diacetone (meth)acrylamide; (4) Norbornene (bicyclo[2.2.1]hepto-2-ene), 5-methylbicyclo[2.2.1]hepto-2-ene, 5-ethylbicyclo[2.2.1]hepto-2- Ene, tetracyclo[4.4.0.12,5.17,10]hepto-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]hepto-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17 ,10]hepto-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]deca-8-ene, tricyclo[5.2.1.02,6]deca-3-ene , Tricyclo[4.4.0.12,5]undeca-3-ene, tricyclo[6.2.1.01,8]undeca-9-ene, tricyclo[6.2.1.01,8]undeca-4-ene, tetra Cyclo[4.4.0.12,5.17,10.01,6]hepto-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]hepto-3-ene, 8-ethylidenetetracyclo[4.4.0.12 ,5.17,12]hepto-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,10.01,6]hepto-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadeca- 4-ene, pentacyclo[7.4.0.12,5.19,12.08,13]pentadeca-3-ene, 5-norbornene-2,3-dicarboxylic anhydride, (meth)acrylic acid anilide, (meth)acryloyl Vinyl compounds such as nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, and vinyltoluene; (5) styrene, α-, o-, m-, p-alkyl group, nitro group, cyano group, amide group derivative of styrene; (6) unsaturated dicarboxylic acid diesters such as diethyl citracate, diethyl maleate, diethyl fumarate, and diethyl itaconic acid; (7) Unsaturated polyacid anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, etc. are mentioned.

Among these, from the viewpoint of availability and reactivity, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) )Acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, (meth)acrylic acid N,N-dimethylamide, (meth )Acrylic morpholine, styrene, vinyl toluene and norbornene are preferred, methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetan-3-yl)methyl(meth)acrylate, styrene and vinyltoluene are more preferred. As the compound (m1-3), one type may be used alone, or two or more types may be used. Among these, from the viewpoint of thermal decomposition resistance and heat yellowing resistance, alkyl (meth)acrylate is preferable, and methyl (meth)acrylate, benzyl (meth)acrylate, and dicyclopentanyl (meth)acrylate are more preferable.

In addition, from the viewpoint of enhancing the solvent resistance, a polymerizable compound having a functional group that reacts with an acidic group is preferred, and specifically, polymerization having a glycidyl group, an oxetanyl group, an isocyanato group, or a block isocyanato group Sex compounds. From the viewpoint of availability and reactivity, glycidyl (meth)acrylate and (3-ethyloxetan-3-yl)methyl methacrylate are more preferable.

As the blocking agent used for the block of the isocyanato group described above, for example, lactam-based blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; methanol and ethanol , Alcohol-based blocking agents such as propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; Butylphenols such as phenol, cresol, xylenol, ethylphenol, o-isopropyl phenol and p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, Phenolic blocking agents such as thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; Active methylene-based blocking agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetyl acetone; Mercaptan-based blocking agents such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; Amine-based blocking agents such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; Acid-amide-based blocking agents such as acetanilide, acetanisidide, acetic acid amide, and benzamide; Acid-imide-based blocking agents such as succinic acid imide and maleic acid imide; Imidazole-based blocking agents such as imidazole, 2-methylimidazole, and 2-ethylimidazole; Urea-based blocking agents such as urea, thiourea, and ethylene urea; Carbamide acid salt-based blocking agents such as phenyl N-phenylcarbamate and 2-oxazolidone; Imine-based blocking agents such as ethylene imine and polyethylene imine; Oxime-based blocking agents such as Formaldoxime, Acetaldoxime, Acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; Bisulfite-based blocking agents, such as sodium bisulfite and potassium bisulfite, are mentioned.

In order to control the weight molecular weight and molecular weight distribution (Mw/Mn) of the resin (B-2) within a specific range and obtain a colored pattern having a desired solvent resistance, the polymerization solvent used in the copolymerization reaction has 3 carbon atoms. It is preferable to contain the hydroxyl group-containing solvent of to 10. As specific examples of the hydroxy group-containing solvent having 3 to 10 carbon atoms, for example, mono, such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, tridecyl alcohol, dodecyl alcohol, benzyl alcohol, etc. Alcohols; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, tri Ethylene 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 monopropyl (Poly)alkylene glycol monoalkyl ethers such as ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. As these C3-C10 hydroxy group-containing solvents, one type may be used alone, or two or more types may be used in combination.

The polymerization solvent used for copolymerization may contain other solvents other than the polymerization solvent. Examples of other solvents include (poly)alkylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Teracetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptane Ketones such as on; 2-hydroxypropionate methyl, 2-hydroxypropionate ethyl, 2-hydroxy-2-methylpropionate methyl, 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl -3-methoxybutylpropionate, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, Esters such as methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; Aromatic hydrocarbons such as toluene and xylene; And carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Among these, from the viewpoint of reactivity, (poly) alkylene glycol monoalkyl ether acetate-based solvents such as propylene glycol monomethyl ether acetate are preferred.

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

The amount of the polymerization solvent used in the copolymerization reaction is not particularly limited, but the sum of the added amounts of the compound (m1-1), compound (m1-2), and compound (m1-3) is 100 parts by weight, preferably It is 30 to 1,000 parts by weight, or 50 to 800 parts by weight.

The polymerization initiator that can be used in this copolymerization reaction is not particularly limited, but, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvale Ronitryl), 2,2'-azobis(isobutyric acid)dimethyl, benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, and the like. As these polymerization initiators, one type may be used alone, or two or more types may be used in combination. The amount of the polymerization initiator used is not particularly limited, but when the total amount of the compound (m1-1), the compound (m1-2), and the compound (m1-3) is 100 parts by weight, the amount of the polymerization initiator is preferably, It is 0.5 to 20 parts by weight, more preferably 1.0 to 10 parts by weight.

In some embodiments, when 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 in this range, the film made of the colored resin composition can obtain a better resolution of the hole pattern.

In some embodiments, the resin (B) is a structural unit having at least one of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and/or at least one of a derivative of (meth)acrylate and/or (meth)acrylate. You may further contain a copolymer consisting of the structural unit which has.

In some embodiments, the resin (B) may occupy about 5 to 25% by weight, preferably 6 to 15% by weight, and more preferably 6 to 10% by weight of the colored resin composition.

In some embodiments, the photopolymerizable monomer (C) is a monomer that can be polymerized by an active radical and/or an acid from which the photopolymerization initiator (D) is generated, for example, but not limited to, (meth)acrylate It is an ethylenically unsaturated bond having the same polymerizable properties as a compound. Here, the compound using parentheses represents the case where the character in the parenthesis exists or does not exist, and for example, in the (meth)acrylate compound, the case of an acrylate compound and a case of a methacrylate compound are included. . The photopolymerizable monomer (C) may also be referred to as a polymerizable compound.

For example, the photopolymerizable monomer (C), although not limited, may include at least one selected from the group consisting of the following options: nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxy Polymerizable compounds having one ethylenically unsaturated bond such as propyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone; 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acrylo) of bisphenol A Polymerizable compounds having two ethylenically unsaturated bonds such as monooxyethyl) ether and 3-methylpentanediol di(meth)acrylate; And trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth) )Acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris( 2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra (Meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. And polymerizable compounds having an ethylenically unsaturated bond. In some embodiments, the photopolymerizable monomer (C) is a polymerizable compound having an ethylenically unsaturated double bond, for example. In some embodiments, the photopolymerizable monomer (C) is a polymerizable compound having, for example, three ethylenically unsaturated double bonds.

Commercially available products of the photopolymerizable monomer (C) include, for example, KAYARAD (registered trademark) DPHA (Nihon Kayaku Co., Ltd.), A-TMM-3LM-N (Shin-Nakamura Chemical Industry Co., Ltd.). ) Company) and A9550 (Shinnakamura Kagakuko teacher), and the like.

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 rate of the photopolymerizable monomer (C) is 100 parts by weight of the solid component, preferably 7 to 65 parts by weight, more preferably 13 to 60 parts by weight, and more preferably 17 to 55 parts by weight. When the content of the photopolymerizable monomer (C) is within the above range, there is a tendency that the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter are improved.

According to some embodiments, the photopolymerization initiator (D) may be a compound capable of initiating a photopolymerization reaction by generating active radicals, acids, etc. by the action of light, and is not particularly limited.

In some embodiments, the photopolymerizable monomer (C) may occupy about 1 to 10% by weight of the colored resin composition.

For example, the photopolymerization initiator (D) is not limited, but may contain at least one selected from the group consisting of the following options: O-acyloxime compound, alkylphenone compound, bisimidazole compound, triazine Compounds, acylphosphine oxide, benzoin compounds, benzophenone compounds, quinone compounds, 10-butyl-2-chloroacridone, benzyl, methylphenylglyoxylate, acetophenone and titanocene compounds.

In some embodiments, it is preferable that the photoinitiator (D) contains at least one selected from the group consisting of the following options: O-acyloxime compound, alkylphenone compound, bis imidazole compound, acetophenone compound , Triazine compounds, acylphosphine oxide compounds, and biimidazole compounds. For example, when the O-acyloxime compound is used as the photopolymerization initiator (D), Irgacure (registered trademark) OXE01 (product of BASF), Irgacure (registered trademark) OXE02 (product of BASF), Commercial products such as N-1919 (made by ADEKA) can be used.

The aforementioned O-acyloxime compound is a compound having a partial structure represented by the following formula (d1). Hereinafter, * represents the coupling end.

As the O-acyloxime compound, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) )Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6- {2-methyl-4-(3 ,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carba Zol-3-yl]-3-cyclopentylpropan-1-one-2-imine, and the like. You may use commercial items such as Irgacure OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) At least one member selected from the group consisting of octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferred, and , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable. When the photoinitiator is these O-acyloxime compounds, there is a tendency for a color filter of high brightness to be obtained.

The above-described alkylphenone compound is a compound having a partial structure represented by the following formula (d2) or a partial structure represented by the formula (d3). Among 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-dimethylamino- 1-(4-morpholinophenyl)-2-benzyl butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl )Phenyl]butan-1-one, and the like. Commercial products such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomers, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

As the triazine compound described above, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl furan -2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5 -Triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis( Trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

Examples of the acylphosphine oxide compound described above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. You may use commercial items, such as Irgacure (registered trademark) 819 (product of BASF).

As the biimidazole compound mentioned above, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Laid-Open Patent Hei 6-75372, Japanese Laid-Open Patent Hei 6-75373, etc. ), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 ,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, Japanese Patent Publication No. 48-38403, Japanese Patent Publication 62 -174204, etc.), imidazole compounds in which the phenyl group at the 4,4' 5,5'-position is substituted by a carboalkoxy group (for example, see Japanese Laid-Open Patent Publication No. Hei 7-10913, etc.) Can be mentioned.

Examples of other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiator (especially amines) described later.

As an acid producing agent, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p -Toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p -Onium salts, such as toluene sulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

The content of the polymerization initiator can be 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, with the total of the resin (B-2) and the polymerizable compound being 100 parts by weight. When the content of the polymerization initiator is within the above range, the sensitivity is improved and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

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

In some embodiments, the solvent (E) may include, but is not limited to, at least one selected from the group consisting of the following options: Ester solvent (here, -COO- is included in the molecule, and -O- Means a solvent that does not contain ), ether solvent (here, it means a solvent that contains -O- in the molecule and does not contain -COO-), ether ester solvent (here, -COO- and -O- in the molecule) Means a solvent containing ), ketone solvent (here, it means a solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (here, OH is included in the molecule, -O-, It means a solvent which does not contain -CO- and -COO-), an aromatic hydrocarbon group solvent, an amide solvent, dimethyl sulfoxide, etc. are mentioned.

As an ester solvent, for example, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isobutyrate Propyl, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

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, and diethylene glycol monoethyl. Ter, 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 Toxic-3-methylbutanol, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether , Anisole, phenetol, and methylanisole.

As a ketone solvent, for example, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

As an alcohol solvent, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, etc. are mentioned, for example.

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

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

The above-described solvent is preferably an organic solvent having a boiling point of 120°C or more and 180°C or less in 1 atm from the viewpoint of coating properties and drying properties. As a solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone and N,N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N -Methylpyrrolidone, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

With respect to the total amount of the colored curable resin composition of the present invention, the content rate of the solvent can be 70 to 95% by weight, more preferably 80 to 90% by weight. In other words, the total content of the solid component of the colored curable resin composition can be 5 to 30% by weight, more preferably 10 to 20% by weight. When the content of the solvent is within the above range, the flatness at the time of application is improved, and the color density is not insufficient when the color filter is formed, so that display characteristics tend to be improved.

In some embodiments, the solvent (E) may contain a first solvent having a relatively high boiling point and a second solvent having a relatively low 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% to 40% by weight of the solvent (E), preferably 5 to 30% by weight, and more preferably 10 to 25% by weight.

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, by using a solvent having a boiling point higher than 150°C and a solvent having a boiling point lower than 150°C in combination, stability and heat resistance of the dye molecule can be improved, and further, the coating layer of the colored resin composition It can be made to have an excellent color development effect.

In some embodiments, the solvent (E) containing the first solvent and the second solvent may occupy about 75 to 90% by weight of the colored resin composition.

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

In some embodiments, the colored resin composition may further contain a leveling agent (F). The leveling agent (F) is a generally well-used coating agent, and can form a flat, smooth, and uniform coating film in the dry film formation process of the paint. Examples of the leveling agent include an organic silicone-based surfactant, a fluorine-based surfactant, and an organic silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the organic silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toresilicone (T-Resilicon) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Tore Dow Corning), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan joint company), etc. .

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M), Megapack (megafack) (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS -718-K (manufactured by DIC), FTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishima Terial Denshi Kasei Co., Ltd.), Suflon (Sa-Flon) ) (Registered trademarks) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.), and the like.

Examples of the organic silicone-based surfactant having a fluorine atom include surfactants having a siloxane chain and a fluorocarbon chain in the molecule. Specifically, Megapack (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be 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 or more and 0.05% by weight or less, based on the total amount of the colored curable resin composition. to be.

In some embodiments, the colored curable resin composition may contain other additives such as a surfactant, a polymerization initiator, a filler, an adhesion promoter, and a light stabilizer.

The polymerization initiator is a compound or a sensitizer used to promote polymerization of a polymerizable compound initiated by a polymerization initiator. When a polymerization initiator is included, it is usually used in combination with a polymerization initiator. As a polymerization initiator, an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxy compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoic acid, and 2-dimethylaminoethyl benzoic acid. , 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine; 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone And the like, and among them, 4,4'-bis(diethylamino)benzophenone is preferred. A commercial product such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) is used. Also works.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. Can be lifted.

Examples of the carboxy compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, And chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

When these polymerization initiators are used, the content of the polymerization initiator is preferably 0.1 to 30 parts by weight when the total of the resin (B-2) and the photopolymerizable monomer (C) (polymerizable compound) is 100 parts by weight. Part may be sufficient, Preferably it may be 1-20 weight part. When the amount of the polymerization initiator is within the above range, a colored pattern can be formed with a higher sensitivity, and the productivity of the color filter tends to be improved.

Another embodiment of the present disclosure relates to a color filter that can be formed of the colored resin composition according to any of the embodiments described above. For example, the colored resin composition according to any of the above-described embodiments can be formed on the color filter by a method such as a photolithography method, an inkjet method, or a printing method, but the present disclosure is limited thereto. no.

As a method of manufacturing a color filter (color filter pattern) by the colored resin composition of the present invention, for example, a photolithography method, an inkjet method, or a printing method may be mentioned. Among these, a photolithography method is preferable. The photolithography method is a method in which the 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, by not using a photomask at the time of exposure and/or not developing, a colored coating film as a cured product of the colored composition layer can be formed. The colored pattern and colored coating film thus obtained can be used as the color filter of the present invention.

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

As a substrate, a glass plate such as quartz glass, borosilicate glass, aluminum oxide silicate glass, soda-lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, aluminum on the substrate , Silver, silver/copper/palladium alloy thin film is used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

The formation of the pattern (pixel) of each color by the photolithography method can be performed with a known or commonly used device or condition. For example, the following manufacturing method can be used.

First, a colored curable resin composition is applied onto a substrate, followed by drying by heating (prebaking) and/or drying under reduced pressure to remove and dry volatile components such as a solvent 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, for example.

Then, the colored composition layer is exposed through a photomask for forming a desired colored pattern. It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate parallel light rays on the entire exposure surface or to accurately align the photomask with the substrate on which the colored composition layer is formed.

It develops by contacting the colored composition layer after exposure with a developer, and a colored pattern is formed on the board|substrate. By development, the unexposed part of the colored composition layer is dissolved in a developer and removed. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethyl ammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight. Moreover, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, or a spray method. Further, the substrate may be inclined at an arbitrary angle during development. After development, it can be washed with water.

Although there is no particular limitation on the dose in the exposure step, since the colored resin composition of the present invention contains the first colorant and the resin (B-2), a fine hole pattern can be obtained even at a higher exposure dose. It is possible. In some embodiments, in the present invention, exposure may be performed at an exposure dose of 50 to 100 mJ. In some embodiments, the distance between the hole edge and the hole after exposure and development may be only 1 to 50 μm, or 3 to 40 μm.

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

According to the colored resin composition of the present invention, a color filter having a fine hole pattern can be produced. This color filter can be used as a color filter or a color wave filter of a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Still another embodiment of the present disclosure relates to a display device that may include, but is not limited to, the aforementioned color filter. 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 include a backlight light source, a TFT substrate, a color filter substrate, and a display medium (for example, a liquid crystal) disposed between the TFT substrate and the color filter substrate, of which a color filter substrate For example, a filter formed from the colored resin composition of the present invention can be used.

Hereinafter, some examples and comparative examples are presented to describe the effects achieved by the colored resin composition according to the embodiment of the present disclosure, and properties of the color resist composition produced using the present disclosure in more detail. However, the following Examples and Comparative Examples are for illustrative purposes only and should not be construed as limiting the present invention. The composition of each of the following Examples and Comparative Examples is as shown in Tables 1 to 3 below. Details of each component are described below. In addition, in the following, "part" represents "weight part" unless there is a special reason.

[Production Example A1- Preparation of first colorant A1-1]

The following reaction was carried out in a nitrogen atmosphere. After adding 32.2 parts of potassium thiocyanate and 160 parts of acetone to a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Then, 50 parts of 2-fluorobenzoyl chloride (manufactured by Tokyo Chemical Co., Ltd.) was dripped over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, after cooling the reaction mixture on ice, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, after cooling the reaction mixture on ice, 34.2 parts of 30% aqueous sodium hydroxide solution was added dropwise. After completion of the dropwise addition, the reaction mixture was further stirred under room temperature for 30 minutes. Then, 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 for 7 hours under heating and refluxing. Next, after standing to cool the reaction mixture to room temperature, the reaction mixture was poured into 120 parts of tap water, 200 parts of toluene was added, and it stirred for 30 minutes. Then, the stirring was stopped and left to stand for 30 minutes, and the organic layer and the aqueous layer were separated. After the aqueous layer was discarded by a 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 saline. An appropriate amount of forget-me-not (i.e., sodium sulfate) was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off the solvent in an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60° C. under reduced pressure to obtain 49.9 parts of a compound represented by the following formula (A1-1-i). The yield was 51%.

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

식 (A1-1-ii)

Formula (A1-1-ii)

The following reaction was carried out in a nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 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 were added, followed by oxychloride. 12.2 parts of phosphorus was added, and the mixture was stirred at 95 to 100°C for 3 hours. Then, the reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. Then, after pouring the diluted reaction mixture into 300 parts of saturated saline, 100 parts of toluene was added and it stirred for 30 minutes. Then, the stirring was stopped and left to stand for 30 minutes, and the organic layer and the aqueous layer were separated. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated saline. After adding an appropriate amount of forget-me-not to the organic layer and stirring for 30 minutes, it was filtered to obtain an organic layer. The obtained organic layer was distilled off the solvent in an evaporator, and a blue-violet solid was obtained. Further, the blue-violet solid was dried at 60° C. under reduced pressure to obtain 18.4 parts of a compound represented by the following formula (A1-1-iii). The yield was 100%.

The following reaction was carried out in a nitrogen atmosphere. 2.0 parts of a compound represented by the formula (A1-1-iii) and 167 parts of ion-exchanged water were added to a flask equipped with a cooling tube and a stirring device, followed by stirring at 40°C for 30 minutes. 5.8 parts of barium chloride dihydrate and 35 parts of ion-exchanged water were added to a beaker, followed by stirring for 30 minutes. An aqueous barium chloride solution was added dropwise to the aqueous solution of the compound represented by the formula (A1-1-iii) prepared first 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, the filtered solid 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 the following formula (A1-1). The yield was 89%.

[Production Example A2- Preparation of first colorant A1-2]

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

식 (A1-2-iii)

Formula (A1-2-iii)

Moreover, (A1-1-iii) in Production Example A1 was changed to the compound of formula (A1-2-iii), and the compound of the following formula (A1-2) was obtained.

[Production Example A3- Preparation of second colorant A2-1]

Into a flask equipped with a cooling tube and a stirring device, 15 parts of a dye represented by the following formula (A2-1-i) (manufactured by Chuga Ikasei), 150 parts of chloroform, and 8.9 parts of N,N-dimethylformamide are added. And, stirring and maintaining at 20 degreeC or less, 10.9 parts of thionyl chlorides were dripped and added. After completion of the dropping, the temperature was raised to 50°C, the reaction was allowed to proceed for 5 hours while maintaining the same temperature, and then cooled to 20°C. A mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise while stirring and maintaining the cooled reaction solution at 20°C or less. It stirred at the same temperature for 5 hours to advance the reaction. Then, using a rotary evaporator, the solvent was distilled off the obtained reaction mixture, a small amount of methanol was added, and it stirred vigorously. While stirring, the mixture was added to a mixed liquid of 375 parts of ion-exchanged water to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60°C, and the following formula (A2-1) (mixture of dye A2-1-a to dye A2-1-h) 11.3 Got wealth:

[Production Example A4-Preparation of second colorant A2-2]

It produced according to the method described in Example 1 of Japanese Laid-Open Patent No. 2016-27075 to obtain a compound of the following formula (A2-2).

[Production Example A5-Preparation of second colorant A2-3]

It was produced according to the method described in Synthesis Example 2 of Japanese Laid-Open Patent No. 2016-176075 to obtain a compound of the following formula (A2-3).

(1) Resin material-1: It was synthesized and obtained. Reference will be made to Production Example 1 below.

[Production Example 1]:

213.6 g of propylene glycol monomethyl ether acetate was put into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, followed by stirring while replacing with nitrogen, and the temperature was raised to 90°C. Then, to a monomer mixture consisting of 20.0 g (0.20 mol) of methyl methacrylate, 88.0 g (0.40 mol) of tricyclodecane methacrylate, and 34.4 g (0.4 mol) of methacrylic acid, t-butylperoxy-2 -What added 4.0 g of ethylhexanoate was dripped into the said flask from a dropping funnel. After completion of the dropwise addition, the mixture was stirred at 95° C. for 3 hours to perform a copolymerization reaction to prepare a copolymer. Then, after replacing the inside of the flask with air, 42.6 g (0.3 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added, and then 120°C. At 6 hours, the ring-opening addition reaction was carried out to prepare a copolymer. Then, 221.3 g of propylene glycol monomethyl ether was added to the reaction solution to obtain a copolymer solution having a solid component concentration of 30% by mass (solid component acid value 30 mgKOH/g, weight average molecular weight 37,100). The copolymer (resin material-1) prepared in Preparation Example 1 has a structural unit represented by the following formula (4).

[Formula 4]

(2) Resin material-2: It was synthesized and manufactured. Reference will be made to Production Examples 2-1 to 2-2 below. Resin B2-1 of Production Example 2-1 and Resin B2-2 of Production Example 2-2 can be used alone or as a resin material-2 by selecting either one.

[Production Example 2-1: Preparation of resin B2-1]

In a flask equipped with a reflux condenser, dropping funnel, thermometer, and stirring device, an appropriate amount of nitrogen gas was flowed to create a nitrogen environment, and 100 parts of propylene glycol monomethyl ether acetate was added, and while stirring, heated to 85°C. . Then, in the flask, over about 5 hours with a dropping pump, 19 parts of methacrylic acid (used to form the constituent units on the lower left), 3,4-epoxycitracyclo[5.2.1.02.6]decane- Mixture of 8-yl acrylate and 3,4-epoxycitracyclo[5.2.1.02.6]decane-9-yl acrylate (50:50 by molar ratio of content) (trade name "E-DCPA", die Cell, Inc.) 171 parts of propylene glycol monomethyl ether acetate were dissolved in 40 parts, and a solution formed therein was added dropwise. In addition, a solution in which 26 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), which is a polymerization initiator, was dissolved in 120 parts of propylene glycol monomethyl ether acetate, was dissolved in a flask using another dropping pump. , It dripped over about 5 hours. After the dropping of the polymerization initiator was completed, the mixture was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (Resin B2-1) of 43.5% solid component. 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 component was 53 mg-KOH/g. The copolymer prepared in Production Example 2-1 has a structural unit represented by the following Chemical Formula 5-1.

[Formula 5-2]

[0279]

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

The inside of a flask equipped with a reflux condenser, a dropping funnel, and a stirrer was replaced in a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate were added, followed by heating to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxycitracyclo[5.2.1.02.6]decane-8-yl acrylate and 3,4-epoxycitracyclo[5.2.1.02]6)decane-9-yl acrylic A mixed solution of 289 parts of a mixture of rates (content ratio is 1:1) and 125 parts of propylene glycol monomethyl ether acetate were added dropwise over 5 hours. Further, 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 completion of the dropwise addition, the mixture was kept at 80°C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B2-2) having a solid component of 35.1% and a viscosity of 125 mPas measured by a type B 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 (in terms of solid component) was 77 mgKOH/g. The copolymer prepared in Production Example 2-2 has a structural unit represented by the following Chemical Formula 5-2.

[Formula 5-2]

(3) Resin material-3: It was synthesized and manufactured. Reference will be made to Production Examples 3-1 to 3-2 below. Resin B3-1 of Production Example 3-1 and Resin B3-2 of Production Example 3-2 may be selected and used alone or as a mixture of resin material-3.

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

Into 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 put, followed by stirring while replacing with nitrogen, and heated to 88°C. Then, to a monomer mixture consisting 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, 2 What added 27.3 g of ,2'-azobis(isobutyric acid)dimethyl (polymerization initiator) was dripped into the flask from a dropping funnel. After completion of the dropwise addition, a copolymerization reaction was performed by stirring at 88°C for 5 hours, and the resin B3-1 (weight average molecular weight: 7100, molecular weight distribution (Mw/Mn): 2.1, acid value: 99 KOH mg/g, silane group equivalent: 1230 g/ ㏖) was obtained.

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

The production method was almost the same as that of Production Example 3-1, except that 3-methacryloyloxypropyltrimethoxysilane was replaced with 68.3 g of 3-methacryloyloxypropyltriethoxysilane. This obtained Resin B3-2.

(4) Photopolymerizable monomer: Dipentaerythritol hexaacrylate ("KAYARAD (registered trademark) DPHA" manufactured by Nihon Kayaku) was used.

(5) Photoinitiator: acetophenone compound (trade name: Tronly PBG327) and O-acyloxime compound (trade name: BASF OXE-01).

(6) Colorant: In the examples in Table 1, C.I. Pigment Blue 15:6 and Xanthone dye are used as colorants; In Examples in Tables 5 to 6, the first colorant and/or the second colorant of the production example is used.

(7) Leveling agent: Polyether-modified silicone oil ("Tore Silicon SH8400" manufactured by Tore Dow Corning).

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

On a 5cm×5cm glass substrate (EAGLE 2000, manufactured by Corning), the prepared colored curable resin composition was applied by spin coating so that the coating thickness was about 1.5 μm to 4.5 μm, and then prebaked at 100°C for 3 minutes. I did. After standing to cool, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), light irradiation at an exposure amount of 80 mJ/cm 2 (365 nm standard) under atmospheric atmosphere, and a series of exposure and development using a photomask The process was performed, and a patterned color filter sample was formed. Then, post-baking was performed for 60 minutes at 230 degreeC in an oven, and the color filter sample was obtained. The volume contraction rate of this sample was measured and the adhesiveness of a color filter and a glass substrate was evaluated. The results of each Example and Comparative Example are as shown in Table 4 below.

As shown in Table 4, when a colored resin composition not according to the embodiment of the present disclosure is used, for example, as shown in the results of Comparative Examples 1 to 3, the colored resin composition does not contain the EDCP monomer unit. If not, the volume contraction rate of the color filter to be formed becomes very large, so that the color filter cannot be satisfactorily adhered to the glass substrate, and thus the heat resistance and stability of the sample of the entire structure formed were relatively inferior.

As shown in Table 4, all of the samples of the color filters formed of the colored resin composition of each Example had good heat resistance and stability. For example, as in Example 3, when the ratio of the number of EDCP monomer units is greater than 40%, the produced color filter has an extremely low shrinkage rate and excellent adhesion.

Each component was mixed in parts by weight shown in Table 5 below to obtain a colored resin composition. In the following Examples and Comparative Examples, 18 parts by weight of a solid component and 82 parts by weight of a solvent are used.

[Production of color filter]

On a square 2-inch glass substrate (#1737; manufactured by Corning), the colored resin composition prepared according to the composition in Table 5 was applied by spin coating, and then prebaked at 100°C for 3 minutes to form a colored composition layer. . After cooling, exposure was performed with an exposure machine (TME-150RSK; manufactured by Topcon) using a photomask (a distance between holes of about 40 µm to 80 µm) in an atmospheric atmosphere and a predetermined exposure amount (365 nm standard). . The exposed colored composition layer was post-baked at 230°C for 20 minutes in an oven to obtain a color filter (film thickness: 2.8 µm).

[Evaluation of completeness of hole pattern]

Each filter formed above was observed with an optical microscope, and it was investigated whether or not a hole pattern was formed in the filter. Results are shown in Tables 5-6.

As can be seen from Comparative Examples A1 and A2 in Table 5, when the colored resin composition does not contain the silicone-containing resin (B-2) of the present invention, a clear hole pattern is formed when the exposure dose is low, When the exposure dose increases, it becomes impossible to form a fine hole pattern.

As can be seen from Examples A1 and A2, the colored resin composition containing other silicone-containing resins B1-1 and B1-2 has the effects of the present invention described above.

As can be seen from Examples A3 to A8, when another first colorant or another second colorant is used, there is no effect on the formation of a hole pattern under a high exposure dose of a color filter to be formed subsequently. Examples A1, A3 using different first colorants; Alternatively, Examples A1, A5, A7, and Examples A3, A6, A8 using other second colorants can form good hole patterns even under high exposure doses.

As shown in Example A4, even a colored resin composition in which the second colorant is not used has the effects of the present invention described above.

We will continue to refer to Table 6. As can be seen from Example A9 in Table 6, the resin (B-1) and the resin (B-2) may be contained in the colored resin composition at the same time. However, when the weight ratio of the resin (B-1) to the solid component is greater than the weight ratio of the resin (B-2) to the solid component (for example, Example A10, the total weight of the resin (B-1) is the resin ( 50% or more of the total weight of B-2)) and the reaction of the colored resin composition under high exposure doses are affected.

As can be seen from Examples A12 and A14 of Table 6, and Examples A13 and A15, the most excellent effect is obtained when the weight ratio of the resin (B-2) to the solid component is within a certain range. When the weight ratio of the resin (B-2) to the solid component is more than 60% by weight and less than 20% by weight, the reaction of the colored resin composition under high exposure dose is affected.

As can be seen from Examples A16 to A19, the section in the preferred range of the other resin (B-2) (for example, the first resin B1-2) is similar to that of the resin B1-1.

In summary, by making the colored resin composition contain the silicone-containing resin of the present invention, the layer formed from the colored resin composition can form a fine and good hole pattern even at a high exposure dose.

Although the present invention was disclosed as above by the above-described embodiment, these do not limit the present invention. Any person having ordinary knowledge in the technical field to which the present invention pertains can make some changes and modifications without departing from the spirit and scope of the present invention. Accordingly, the scope of protection of the present invention is based on what is defined in the claims to be described later.

Claims (12)

As a colored resin composition,
coloring agent;
A resin comprising an epoxy dicyclopentenyl group monomer unit and a silane monomer unit, wherein the silane monomer unit has a structure represented by the following formula (3):
[Formula 3]

(In the formula, 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 (however, at least one of R5 to R7 is 1 carbon atom) It is an alkoxy group of to 6); p is a positive integer, q is an integer of 1 to 10);
Photopolymerizable monomers;
Photopolymerization initiator; And
solvent
Containing a colored resin composition. The colored resin composition according to claim 1, wherein the number of the epoxydicyclopentenyl monomer units accounts for 8% to 50% of the total number of all monomer units in the resin. The method according to claim 1, wherein the ratio of the number of the epoxydicyclopentenyl monomer units and the number of the silane monomer units is 1:0.02 to 1:0.08; Or the silane monomer unit is 2 parts by weight to 8 parts by weight, based on 100 parts by weight of the epoxy dicyclopentenyl monomer unit. The method of claim 1, wherein the epoxy dicyclopentenyl monomer unit is at least one of a first monomer unit having a structure represented by Formula 1 below, and a second monomer unit having a structure represented by Formula 2 below. A colored resin composition comprising:
[Formula 1]

(In the formula, R1 represents 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 with a hydroxy group, and X1 is a single bond, -R3-, -R3-O-, Represents -R3-S- or -R3-NH-, wherein R3 represents an alkylene group having 1 to 6 carbon atoms, and n is a positive integer);
[Formula 2]

(In the formula, R2 represents 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 with a hydroxy group, and X2 is a single bond, -R3-, -R3-O-,- R3-S- or -R3-NH- is represented, and m is a positive integer.) The colored resin composition according to claim 1, wherein the epoxydicyclopentenyl monomer unit comprises a monomer unit having a structure represented by the following formula 1A and a monomer unit having a structure represented by the following formula 2A:
[Formula 1A]

[Formula 2A]

. The colored resin composition according to claim 1, wherein the silane monomer unit has a structure represented by the following formula 3A or 3B:
[Chemical Formula 3A]

[Chemical Formula 3B]

. As a colored resin composition,
Solid ingredients; And
solvent
Including,
The solid component,
A first colorant;
First resin;
Polymerizable compounds; And
Polymerization initiator
Including,
The first colorant comprises a compound of the structure represented by the following formula (I):

(In formula (I), R ⁴¹ to R ⁴⁴ are each independently 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 7 to carbon atoms which may have a substituent. Represents an aralkyl group of 30, and the aromatic hydrocarbon group and the substituent which may have the aralkyl group include -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , and hydrogen contained in the saturated hydrocarbon group The atom may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH ₂ -contained in the saturated hydrocarbon group is at least one of -O- and -CO- It may be substituted with one (however, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent -CH ₂ -is not simultaneously substituted with -O-, and -CH ₂ -at the terminal is -O- or -CO- Not substituted with), R ⁴¹ and R ⁴² may be bonded to each other and form a ring with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ are bonded to each other and at the same time, the nitrogen atom to which they are bonded and May form a ring together;
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, -CH ₂ -constituting the alkyl group may be substituted with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² are bonded to each other to form -NH-, -S- or -SO _2- (However, in the alkyl group, adjacent -CH ₂ -is not simultaneously substituted with -O-, and the terminal -CH ₂ -is not substituted with -O- or -CO-);
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms, and the aromatic heterocycle has a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent May be present, and the substituent group which the aromatic hydrocarbon group may have includes -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f ;
M ^r+ is a hydrogen ion, an r-valent metal ion, or a substituted or unsubstituted ammonium ion;
k is the sum of the number of -SO ₃ of R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ and the number of -SO ₂ -N ^-- SO ₂ -R ^f ;
r represents an integer of 1 or more;
R ^f is a fluoroalkyl group having 1 to 12 carbon atoms) (provided that R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ are at least one of -SO ₃ ^- or -SO ₂ -N ^-- SO _2- R ^f );
A colored resin composition in which the first resin contains a structural unit (b1-1) represented by the following formula (1b);

(In formula (1b), R4 represents a hydrogen atom or a methyl group;
Each of R5 to R7 independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;
p is a positive integer, and q is an integer from 1 to 10;
However, at least one of R5 to R7 is an alkoxy group having 1 to 6 carbon atoms). The colored resin composition according to claim 7, wherein the solid component further comprises a second colorant, and the second colorant comprises a compound having a structure represented by the following formula (II):

(In formula (II), R ¹¹ to R ¹⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or -R ²⁰ -Si(R ¹⁹ ) ₃ ;
The hydrogen atom of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom, and -CH ₂ -in the saturated hydrocarbon group is -O-, -CO-, -NR ²¹ -, -OCO- , -COO-, -OCONH-, -CONH- or -NHCO- may be substituted;
However, in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, adjacent -CH ₂ -is not substituted at the same time, and -CH ₂ -at the terminal is not substituted;
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 selected from _{^{-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 monovalent saturated hydrocarbon group having 1 to 20 carbon atoms The hydrogen atom of the group may be substituted with a halogen atom;
Z ⁺ is [N(R ²⁶ ) ₄ ] ⁺ , Na ⁺ or K ⁺ ; Each of the four R ²⁶ is 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;
n is an integer from 0 to 4;
-R ²⁰ -Si (R ¹⁹⁾ 3 of the _three R ¹⁹ each independently represent a hydrogen atom, a hydroxyl group, having 1 to 4 carbon alkyl group or an alkoxy group having 1 to 4 carbon atoms in the; R ²⁰ is an alkylene group having 1 to 10 carbon atoms, and -CH ₂ -in the alkylene group constituting R ²⁰ is -O-, -CO-, -NR ²¹ -, -OCO-, -COO-, -OCONH- , -CONH- or -NHCO- may be substituted;
a is 0 or 1). The method according to claim 7, wherein the first resin is a copolymer containing the structural unit (b1-1), the structural unit (b1-2), and the structural unit (b1-3);
The structural unit (b1-2) is composed of a polymerizable unsaturated compound having an acidic group;
The structural unit (b1-3) is a structural unit different from the structural unit (b1-1) and the structural unit (b1-2);
When the sum of all the structural units of the copolymer is 100 mol%, the structural unit (b1-1) occupies 1 to 50 mol%. The method of claim 7, wherein the solid component further comprises a second resin, wherein the second resin is an alkali-soluble resin that does not contain silicone, and the weight ratio of the second resin to the solid component is the first resin Is smaller than the weight ratio occupied by the solid component. A color filter formed from the colored resin composition according to any one of claims 1 to 10. A display device comprising the color filter according to claim 11.