Compound and coloring composition

文档序号：1038263 发布日期：2020-10-30 浏览：37次中文

阅读说明：本技术 化合物和着色组合物 (Compound and coloring composition ) 是由大家健一郎朴廷烋于 2020-04-24 设计创作，主要内容包括：本发明提供新型化合物和着色组合物。式(I)表示的化合物。[式(I)中,Q表示式(Q1)：*－CR6＝CR5－NR3－**、式(Q2)：*－O－CR5＝N－**、式(Q3)：*－S－CR5＝N－**、式(Q4)：*－N＝CR5－NR3－**或式(Q5)：*－NR6－CR5＝N－**表示的基团(*表示与R4所键合的碳原子的键合位点)。R1～R5各自独立地表示氢原子或可以具有取代基的碳原子数1～6的1价烃基,该烃基中含有的－CH2－可以被取代为－O－或－CO－。R6表示可以具有取代基的1价芳香族基团或可以具有取代基的碳原子数1～6的1价脂肪族烃基,该脂肪族烃基中含有的－CH2－可以被取代为－O－或－CO－。]<Image he="277" wi="700" file="DDA0002465213760000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention provides a novel compound and a coloring composition. A compound represented by the formula (I). [ in the formula (I), Q represents formula (Q1): (xi-CR) 6 ＝CR 5 －NR 3 -, formula (Q2): O-CR 5 N-x, formula (Q3): S-CR 5 N-x, formula (Q4): -N ═ CR 5 －NR 3 Or formula (Q5): -NR 6 －CR 5 A group represented by ═ N — (. indicates a group represented by R) 4 The bonding site of the bonded carbon atom). R 1 ～R 5 Each independently represents a hydrogen atom or a C1-6 valent hydrocarbon group which may have a substituent, the hydrocarbon group containing-CH 2 -may be substituted by-O-or-CO-. R 6 Represents an optionally substituted 1-valent aromatic group or an optionally substituted 1-valent aliphatic hydrocarbon group having 1 to 6 carbon atoms and containing-CH 2 -may be substituted by-O-or-CO-.])

1. A compound represented by the formula (I),

in the formula (I), the compound is shown in the specification,

q represents formula (Q1): (xi-CR)⁶＝CR⁵－NR³-, formula (Q2): O-CR⁵＝N

-, formula (Q3): S-CR⁵N-x, formula (Q4): -N ═ CR⁵－NR³Or formula (Q5): -NR⁶－CR⁵A group represented by ═ N —, wherein —, represents a group represented by R⁴The bonding site of the carbon atom to which it is bonded,

R¹～R⁵each independently represents a hydrogen atom or a carbon which may have a substituentA 1-valent hydrocarbon group having 1 to 6 atoms, the hydrocarbon group containing-CH₂-may be substituted by-O-or-CO-,

R⁶represents an optionally substituted 1-valent aromatic group or an optionally substituted 1-valent aliphatic hydrocarbon group having 1 to 6 carbon atoms and containing-CH ₂-may be substituted by-O-or-CO-.

2. A coloring composition comprising a colorant and a resin, the colorant containing the compound of claim 1.

3. A colored curable resin composition comprising the colored composition according to claim 2, a polymerizable compound, and a polymerization initiator.

4. A color filter formed from the colored composition according to claim 2 or the colored curable resin composition according to claim 3.

5. A display device comprising the color filter of claim 4.

Technical Field

The present invention relates to novel compounds and coloring compositions.

Background

Various dyes are known as colorants contained in colored resin compositions for forming color filters included in liquid crystal display devices, solid-state imaging elements, and the like. Patent document 1 discloses a filter for a plasma display panel using a squarylium dye.

Disclosure of Invention

The purpose of the present invention is to provide a compound having an excellent absorbance retention rate before and after a light resistance test, a colored composition containing the compound, a colored curable resin composition containing the colored composition, a color filter formed from these compositions, and a display device including the color filter.

The invention provides a compound, a colored composition, a colored curable resin composition, a color filter and a display device shown below.

A compound represented by the formula (I).

[ in the formula (I),

q represents formula (Q1): (xi-CR)⁶＝CR⁵－NR³-, formula (Q2): O-CR⁵N-x, formula (Q3): S-CR⁵N-x, formula (Q4): -N ═ CR⁵－NR³Or formula (Q5): -NR⁶－CR⁵A group represented by ═ N — (. indicates a group represented by R)⁴The bonding site of the bonded carbon atom).

R¹～R⁵Each independently represents a hydrogen atom or a C1-6 valent hydrocarbon group which may have a substituent, the hydrocarbon group containing-CH₂-may be substituted by-O-or-CO-.

R⁶Represents an optionally substituted 1-valent aromatic group or an optionally substituted 1-valent aliphatic hydrocarbon group having 1 to 6 carbon atoms and containing-CH ₂-may be substituted by-O-or-CO-.]

Note that, denotes a bonding site on the other side of Q.

[ 2 ] A coloring composition comprising a resin and a colorant comprising the compound of [ 1 ] above.

[ 3 ] A colored curable resin composition comprising the colored composition according to [ 2 ] above, a polymerizable compound, and a polymerization initiator.

A color filter comprising the colored composition according to [ 2 ] or the colored curable resin composition according to [ 3 ].

A display device comprising the color filter according to the above [ 4 ].

The coloring composition containing the compound of the present invention is excellent in absorbance retention before and after a light resistance test.

Drawings

Fig. 1 (a) and (b) are schematic cross-sectional views showing an example of an optical filter.

Fig. 2 (a) is a schematic cross-sectional view showing an example of an organic EL display device using an optical filter, and (b) is a schematic cross-sectional view showing an example of a liquid crystal display device using an optical filter.

Description of the symbols

1, 2 image display elements, 10 optical filters, 11 image display element adhesive layers, 12 phase difference films, 13 adhesive layers, 14 st protective films, 15 polarizing films, 16 nd protective films, 2 nd protective films, 20 optical filters, 21 image display element adhesive layers, 24 st protective films, 1 st protective films, 25 polarizing films, 26 nd protective films.

Detailed Description

(Compound represented by the formula (I))

The present invention relates to a compound represented by the following formula (I) (hereinafter, may be referred to as "compound (I)").

In the formula (I), all symbols have the same meanings as described above. ]

In the compound (I), when Q is a group represented by the formula (Q1), the compound (I) has the following structure.

In the compound (I), when Q is a group represented by the formula (Q2), the compound (I) has the following structure.

In the compound (I), when Q is a group represented by the formula (Q3), the compound (I) has the following structure.

In the compound (I), when Q is a group represented by the formula (Q4), the compound (I) has the following structure.

In the compound (I), when Q is a group represented by the formula (Q5), the compound (I) has the following structure.

The compound (I) is excellent in absorbance retention before and after a light resistance test when used in a colored composition described later, for example. The compound (I) is also excellent in heat resistance when it is used for, for example, a coloring composition.

In the compound (I) in which Q is a group represented by the formula (Q1), in addition to the description of the structure, for example, a tautomer of a resonance structure represented by the following formula exists.

In the compound (I) in which Q is a group represented by the formula (Q2), in addition to the description of the structure, for example, a tautomer of a resonance structure represented by the following formula exists.

In the compound (I) in which Q is a group represented by the formula (Q3), in addition to the description of the structure, for example, a tautomer of a resonance structure represented by the following formula exists.

In the compound (I) in which Q is a group represented by the formula (Q4), in addition to the description of the structure, for example, a tautomer of a resonance structure represented by the following formula exists.

In the compound (I) in which Q is a group represented by the formula (Q5), in addition to the description of the structure, for example, a tautomer of a resonance structure represented by the following formula exists.

The compound (I) includes the tautomers exemplified above, and includes all tautomers.

The hydrocarbon group in the formula (I) means a group composed of a carbon atom and a hydrogen atom, and the number of carbon atoms of the hydrocarbon group includes the number of carbon atoms of the substituent.

-CH contained in hydrocarbon group₂The number of carbon atoms of the group after the substitution with-O-or-CO-means the number of carbon atoms before the substitution with-O-or-CO-.

In the formula (I), as R¹～R⁵In the (C1-C6) 1-valent hydrocarbon group, a 1-valent aliphatic hydrocarbon group or a 1-valent aromatic hydrocarbon group is mentioned.

R¹～R⁵The 1-valent aliphatic hydrocarbon group in (1) may be a 1-valent aliphatic saturated hydrocarbon group or a 1-valent aliphatic unsaturated hydrocarbon group. The 1-valent aliphatic hydrocarbon group may be a straight-chain or branched-chain hydrocarbon group, or may be an alicyclic hydrocarbon group.

As R¹～R⁵The 1-valent aliphatic saturated hydrocarbon group in (1) includes a linear alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a branched alkyl group having 3 to 6 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, and a neopentyl group; and alicyclic saturated hydrocarbon groups having 3 to 6 carbon atoms such as cyclopropyl, cyclopentyl and cyclohexyl.

As R¹～R⁵The 1-valent aliphatic unsaturated hydrocarbon group in (A) includes a linear chain of 2 to 6 carbon atoms such as an ethylene group, a propylene group, a butenyl group, a pentenyl group, a hexenyl group and the likeAn alkenyl group; a branched alkenyl group having 4 to 6 carbon atoms such as a secondary butenyl group and an isobutenyl group; a straight chain alkynyl group having 3 to 6 carbon atoms such as a propynyl group, an n-butynyl group, an n-pentynyl group, and an n-hexynyl group; branched alkynyl having 4 to 6 carbon atoms such as sec-butynyl and iso-butynyl; a cycloalkenyl group having 3 to 6 carbon atoms such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group; and cycloalkynyl groups having 4 to 6 carbon atoms such as a cyclobutynyl group, a cyclopentynyl group, and a cyclohexynyl group.

R¹～R⁵When the 1-valent aliphatic hydrocarbon group in (1) contains a cyclic structure, the number of carbon atoms constituting the cyclic structure is preferably 3 to 6, more preferably 5 or 6.

As R ¹～R⁵As the 1-valent aromatic hydrocarbon group in (1), a phenyl group is mentioned.

In the formula (I), as R¹～R⁵Examples of the substituent which the hydrocarbon group in (3) may have include a halogen atom, a hydroxyl group, an amino group, a nitro group, a sulfamoyl group, and a sulfo group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R¹～R⁵The substituent which the hydrocarbon group in (1) may have is preferably a halogen atom.

In the formula (I), the C1-6 valence alkyl contains-CH₂-may be substituted by-O-or-CO-. Examples of such a group include — C (═ O) CH₃、－C(＝O)－OCH₂CH₃。

In the formula (I), R¹And R²Each independently is preferably a hydrogen atom or an alkyl group, more preferably both hydrogen atoms.

R³～R⁵Each independently is preferably a hydrogen atom or an alkyl group. R³More preferably a hydrogen atom, R⁴And R⁵More preferably each independently is an alkyl group.

In the formula (I), R⁶The 1-valent aromatic group in (b) may be a 1-valent aromatic hydrocarbon group or a 1-valent aromatic heterocyclic group. The 1-valent aromatic group may have a monocyclic structure or a condensed ring structure.

The number of carbon atoms of the 1-valent aromatic hydrocarbon group is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 13.

The 1-valent aromatic hydrocarbon group includes aryl groups having 6 to 16 carbon atoms such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, propylphenyl, butylphenyl, hexylphenyl, 2-ethylhexylphenyl, naphthyl, biphenyl, terphenyl, propylbiphenyl, anthracenyl, phenanthrenyl, pyrenyl and fluorenyl; aralkyl groups such as benzyl, phenethyl, phenylpropyl, and phenylbutyl.

The 1-valent aromatic hydrocarbon group includes a group in which hydrogen bonded to a carbon of an aromatic ring constituting the aromatic hydrocarbon group is substituted with an alkyl group or an aryl group, and-CH contained in the substituted alkyl group₂-may be substituted by-O-or-CO-.

Form R⁶The number of carbon atoms of the aromatic ring contained in the 1-valent aromatic hydrocarbon group in (1) is preferably 6 to 18, and more preferably 6 to 12.

The number of carbon atoms of the 1-valent aromatic heterocyclic group is usually 2 to 30, preferably 4 to 20, and more preferably 4 to 10.

The hetero atom in the 1-valent aromatic heterocyclic group represents a nitrogen atom, an oxygen atom, a sulfur atom or the like. The heteroatom contained in the 1-valent aromatic heterocyclic group is preferably 1 to 3, and more preferably 1.

Examples of the 1-valent aromatic heterocyclic group include those derived from furan, thiophene, pyrrole,Oxazole, isoOxazole, thiazole, isothiazole, imidazole, pyrazole, furazan, triazole, and mixtures thereof,Diazole, isoOxazole, tetrazole, pyran, pyridine, thiopyran, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, thiopyran, pyridazine, pyrimidine, pyrazine, triazine, benzofuran, benzothiophene, indole, and indole,Isoindole, indolizine, isoindoline, chromene, isochromene, chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolizine, benzimidazole, benzothiazole, benzothiadiazole, indazole, naphthyridine, quinoxaline, quinazoline (quinazolidine), cinnoline, phthalazine, porphyrin, pteridine, carbazole, xanthene, phenanthridine, acridine, beta-carboline, perimidine, phenanthroline, thianthrene, thiophene Thiophene and thiophene

A group obtained by removing 1 hydrogen atom from a heterocyclic compound such as oxazine, phenothiazine, phenazine, etc.

The 1-valent aromatic heterocyclic group includes a group in which hydrogen contained in the above group is substituted with a hydrocarbon group such as an alkyl group or an aryl group.

Form R⁶The number of carbon atoms of the aromatic heterocyclic group contained in the 1-valent aromatic heterocyclic group in (1) is preferably 6 to 18, more preferably 6 to 12.

In the formula (I), as R⁶Examples of the substituent which the aromatic group in (3) may have include a halogen atom, a hydroxyl group, an amino group, a nitro group, an aryloxy group, an arylcarbonyl group, an aryloxycarbonyl group, a carboxyl group, a carbamoyl group, a sulfamoyl group, and a sulfo group.

In the formula (I), R⁶The 1-valent aliphatic hydrocarbon group in (1) may be a 1-valent aliphatic saturated hydrocarbon group or a 1-valent aliphatic unsaturated hydrocarbon group. The 1-valent aliphatic hydrocarbon group may be a straight-chain or branched-chain hydrocarbon group, or may be an alicyclic hydrocarbon group.

R⁶The number of carbon atoms of the 1-valent aliphatic hydrocarbon group in (A) is usually 1 to 20, preferably 1 to 15, more preferably 1 to 10, and further preferably 1 to 6. When the 1-valent aliphatic hydrocarbon group contains a cyclic structure, the number of carbon atoms constituting the cyclic structure is preferably 3 to 6, more preferably 5 or 6.

R⁶The 1-valent aliphatic hydrocarbon group in (1) may be a 1-valent aliphatic saturated hydrocarbon group or a 1-valent aliphatic unsaturated hydrocarbon group. The 1-valent aliphatic hydrocarbon group may be linear or branched The chain hydrocarbon group may be an alicyclic hydrocarbon group.

As R⁶The 1-valent aliphatic saturated hydrocarbon group in (1) includes a linear alkyl group having 1 to 16 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; a branched alkyl group having 3 to 16 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group; cycloalkyl groups having 3 to 16 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclopentenyl; alkylcycloalkyl groups having 4 to 16 carbon atoms such as propylcyclohexyl and octylcyclohexyl; c4-16 cycloalkylalkyl groups such as cyclohexylbutyl and cyclohexyloctyl.

As R⁶The 1-valent aliphatic unsaturated hydrocarbon group in (a) includes a linear alkenyl group having 2 to 16 carbon atoms such as a vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, and the like; branched alkenyl groups such as a secondary butenyl group and an isobutenyl group; a linear alkynyl group having 4 to 16 carbon atoms such as a propynyl group, an n-butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptynyl group, an n-octynyl group, an n-nonynyl group, an n-decynyl group, etc.; a branched alkynyl group having 4 to 16 carbon atoms such as an s-butynyl group and an i-butynyl group; a cycloalkenyl group having 3 to 16 carbon atoms such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, or the like; an alkenyl cycloalkyl group having 5 to 16 carbon atoms such as a propenyl cyclohexyl group and a 1-decenyl cyclohexyl group; and a cycloalkynyl group having 4 to 16 carbon atoms such as a cyclobutynyl group, a cyclopentynyl group, and a cyclohexynyl group.

As R⁶The 1-valent aliphatic unsaturated hydrocarbon group in (a) includes a linear alkenyl group having 2 to 16 carbon atoms such as a vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, and the like; branched alkenyl groups such as a secondary butenyl group and an isobutenyl group; a linear alkynyl group having 4 to 16 carbon atoms such as a propynyl group, an n-butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptynyl group, an n-octynyl group, an n-nonynyl group, an n-decynyl group, etc.; a branched alkynyl group having 4 to 16 carbon atoms such as an s-butynyl group and an i-butynyl group; a cycloalkenyl group having 3 to 16 carbon atoms such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, or the like; c3An alkenyl cycloalkyl group having 5 to 16 carbon atoms such as an alkenyl cyclohexyl group and a 1-decenyl cyclohexyl group; and a cycloalkynyl group having 4 to 16 carbon atoms such as a cyclobutynyl group, a cyclopentynyl group, and a cyclohexynyl group.

R⁶When the 1-valent aliphatic hydrocarbon group (b) has a cyclic structure, the number of carbon atoms constituting the cyclic structure is preferably 3 to 8, more preferably 4 to 6.

In the formula (I), as R⁶Examples of the substituent which may be contained in the aliphatic hydrocarbon group include R¹～R⁵The substituents exemplified in (1).

As R⁶The substituent which the hydrocarbon group in (1) may have is preferably a halogen atom.

R⁶In (2) — CH contained in the aliphatic hydrocarbon group₂-may be substituted by-O-or-CO-. Examples of such a group include — C (═ O) CH₃，－C(＝O)－OCH₂CH₃。

Examples of the compound (I) include compounds represented by the following formula.

(Process (1) for producing Compound (I))

The compound (I) of the present invention can be obtained by first reacting a compound represented by the following formula (IV-1) (hereinafter, sometimes referred to as "compound (IV-1)") with a compound represented by the following formula (IV-2) (hereinafter, sometimes referred to as "compound (IV-2)") to obtain a compound represented by the following formula (IV-3) (hereinafter, sometimes referred to as "compound (IV-3)") and then obtaining a compound represented by the following formula (IV-4) (hereinafter, sometimes referred to as "compound (IV-4)") from the compound (IV-3). Then, this compound (IV-4) is reacted with a compound represented by the following formula (IV-5) (hereinafter, may be referred to as "compound (IV-5)") to produce compound (I).

[ formula (IV-1) and formula (IV-3) wherein R⁷And R⁸Each independently represents an alkoxy group having 1 to 20 carbon atoms.

In the formulae (IV-2), (IV-3) and (IV-4), R³～R⁶The same meanings as described above are indicated.

In the formula (IV-5), R¹And R ²The same meanings as described above are indicated.]

In the formulae (IV-1) and (IV-3), as R⁷And R⁸Examples of the alkoxy group having 1 to 20 carbon atoms in the group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentoxy group, an isopentoxy group, a neopentoxy group, a n-hexoxy group, a n-cyclohexoxy group, and a n-dodecoxy group.

Examples of the compound (IV-1) include compounds represented by the following formula.

Examples of the compound (IV-2) include compounds represented by the following formula.

Examples of the compound (IV-3) include compounds represented by the following formula.

Examples of the compound (IV-4) include compounds represented by the following formula.

Examples of the compound (IV-5) include compounds represented by the following formula.

In the step of producing the compound (IV-3), the compound (IV-1) and the compound (IV-2) are preferably reacted in an organic solvent.

Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; hydrocarbon solvent such as hexane, cyclohexane and decalin, tetrahydrofuran and 1, 4-bis

Ether solvents such as alkane and dimethoxyethane; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform and the like; alcohol solvents such as methanol, ethanol, isopropanol, butanol, etc.; nitrohydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; amide solvents such as N, N-dimethylformamide and 1-methyl-2-pyrrolidone, and the like may be used in combination. Among them, butanol is preferred. The amount of the organic solvent to be used is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, based on 1 part by mass of the compound (IV-1).

The amount of the compound (IV-2) used in the step of producing the compound (IV-3) is preferably 0.7 to 3mol, more preferably 1 to 2mol, based on 1mol of the compound (IV-1).

The reaction temperature is preferably from 30 ℃ to 180 ℃, more preferably from 80 ℃ to 140 ℃. The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

In the step of producing the compound (IV-4), it is preferable to reflux the compound (IV-3) in an acidic aqueous solution using hydrochloric acid, acetic acid or the like.

The reaction temperature is preferably from 30 ℃ to 180 ℃, more preferably from 80 ℃ to 140 ℃. The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

In the step of producing the compound (I), it is preferable to react the compound (IV-4) and the compound (IV-5) in an organic solvent from the viewpoint of yield.

The organic solvent includes the above-exemplified organic solvents, and among them, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent to be used is preferably 10 to 200 parts by mass, more preferably 20 to 160 parts by mass, based on 1 part by mass of the total of the compound (IV-4) and the compound (IV-5).

The amount of the compound (IV-5) used in the step of producing the compound (I) is preferably 0.7 to 3mol, more preferably 1 to 2mol, based on 1mol of the compound (IV-4).

The reaction temperature is preferably from 30 ℃ to 180 ℃, more preferably from 80 ℃ to 140 ℃. The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

The method for obtaining the compound (I) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a method of cooling and then collecting precipitated crystals by filtration is mentioned. The crystals collected by filtration are preferably washed with water or the like, followed by drying. Further, if necessary, further purification may be carried out by a known method such as recrystallization and column chromatography.

(Process (2) for production of Compound (I))

The compound (I) of the present invention can be produced by a method in which the compound (IV-2), the compound (IV-5) and a squaric acid (3, 4-dihydroxy-3-cyclobutene-1, 2-dione) represented by the following formula (IV-6) are reacted with each other.

As the compound (IV-2) and the compound (IV-5), the compounds described above can be used.

In the step of producing the compound (I), a method of subjecting the compound (IV-2), the compound (IV-5) and squaric acid to dehydration condensation in an organic solvent is preferably employed from the viewpoint of yield.

The amount of the squaric acid used in the step of producing the compound (I) is preferably 0.45 to 0.6mol, more preferably 0.47 to 0.55mol, based on 1mol of the total of the compound (IV-2) and the compound (IV-5).

The reaction temperature is preferably from 30 ℃ to 180 ℃, more preferably from 80 ℃ to 140 ℃. The reaction time is preferably 1 to 20 hours, more preferably 3 to 15 hours.

The method for obtaining the compound (I) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed, and examples thereof include the above-mentioned methods.

(coloring composition)

The coloring composition of the present invention comprises a colorant (a) containing a compound (I) and a resin (B). The coloring composition may further contain a solvent (E), a leveling agent (F), and the like. In the present specification, the compounds exemplified as the respective components may be used alone or in combination of a plurality of them unless otherwise specified.

The coloring composition of the present invention is excellent in absorbance retention before and after a light resistance test. The coloring composition is also excellent in heat resistance.

(colorant (A))

The colorant (a) contained in the coloring composition may contain another dye as the dye (a1) in addition to the compound (I). Examples of such dyes include oil-soluble dyes, acid dyes, amine salts of acid dyes, and dyes such as sulfonamide derivatives of acid dyes, and examples thereof include compounds classified into dyes of solvent, acid, basic, reactive, direct, disperse, mordant, or reducing types in The color index (published by The Society of Dyers and Colourists), and known dyes described in notes on dyeing (Dyers). Further, depending on the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. These dyes may be used alone or in combination of 2 or more.

Specifically, c.i. solvent yellow 4 (hereinafter, the description of c.i. solvent yellow is omitted, and only the number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

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

c.i. solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

c.i. solvent blue 14, 18, 35, 36, 45, 58, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

c.i. solvent green 1,3,5, 28, 29, 32, 33; and the like, the c.i. solvent dye,

c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212,214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

c.i. acid red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;

c.i. acid green 3, 5, 9, 25, 27, 28, 41;

c.i. acid violet 34, 120;

c.i. acid blue 25, 27, 40, 45, 78, 80, 112; etc., c.i. acid dye, c.i. basic green 1; and the like, a basic dye,

c.i. reactive yellow 2, 76, 116;

c.i. reactive orange 16; and the like, c.i. reactive dyes,

c.i. direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. direct blue 40; and the like, the direct dye is directly used,

c.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

c.i. disperse blue 1, 14, 56, 60; and the like, the C.I. disperse dye,

as the c.i. mordant dye, c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; and the like C.I. mordant dyes,

C.i. vat dyes such as c.i. vat green 1, and the like.

The content of the compound (I) in the dye (a1) is preferably 3 to 100 parts by mass, more preferably 10 to 70 parts by mass, and still more preferably 15 to 50 parts by mass, based on 100 parts by mass of the total amount of the dye (a 1). When the content of the compound (I) is within the above range, high color reproducibility is obtained in the production of a color filter, and the film tends to be easily formed.

The colorant (a) contained in the coloring composition preferably contains a pigment (a 2). The pigment (a2) is not particularly limited, and a known pigment can be used. For example, pigments classified as pigments in The color index (published by The Society of Dyers and Colourists) may be mentioned, and these may be used alone or in combination of 2 or more.

Examples of the pigment (a2) include yellow pigments such as c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

Red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;

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

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

green pigments such as c.i. pigment green 7, 36, 58;

c.i. brown pigments such as pigment brown 23, 25; and

c.i. pigment black 1, 7 and the like.

As the pigment (a2), preferred are yellow pigments such as c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and the like; green pigments such as c.i. pigment green 7, 36, 58, more preferably c.i. pigment yellow 138, 150, 185 and c.i. pigment green 58, and further preferably c.i. pigment yellow 138 and c.i. pigment green 58. By containing the pigment, the transmittance spectrum can be easily optimized, and the light resistance and the chemical resistance of the color filter can be improved.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment of the pigment surface with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method or the like, cleaning treatment with an organic solvent or water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like, as required.

The pigment is preferably uniform in particle size. The pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by performing the dispersion treatment by containing the pigment dispersant.

Examples of the pigment dispersant include surfactants, which may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, there may be mentioned polyester, polyamide, acrylic and other surfactants. These pigment dispersants may be used alone, or 2 or more kinds may be used in combination. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (registered trademark) (manufactured by BASF Co., Ltd.), AJISPER (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Co., Ltd.), and the like.

When a pigment dispersant is used, the amount thereof is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the total amount of the pigments (a 2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

When the pigment (a2) is contained, the content ratio of the dye (a1) to the pigment (a2) in the colorant (a) is usually 45:55 to 1:99, preferably 40:60 to 2:98, and more preferably 38:62 to 3:97 on a mass basis.

The content of the colorant (a) is preferably 5 to 60 parts by mass, more preferably 8 to 55 parts by mass, and still more preferably 10 to 50 parts by mass, based on 100 parts by mass of the solid content of the coloring composition. When the content of the colorant (a) is within the above range, the color density in the production of a color filter is sufficient, and a desired amount of the resin (B) and the like can be contained in the coloring composition, so that the film can be easily formed. Here, the "solid component" in the present specification means a substance obtained by removing a solvent from a coloring composition. The total amount of the solid components and the content of each component relative to the total amount of the solid components can be measured by a known analytical means such as liquid chromatography or gas chromatography.

(resin (B))

The resin (B) contained in the coloring composition is not particularly limited, and is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [ K1] to [ K6 ].

A resin [ K1] which is a copolymer of at least 1 (Ba) (hereinafter, sometimes referred to as "(Ba)") selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and a monomer (Bb) (hereinafter, sometimes referred to as "(Bb)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

Resins [ K2] (Ba) and (Bb) and a monomer (Bc) copolymerizable with (Ba) (which is different from (Ba) and (Bb)) (hereinafter, sometimes referred to as "(Bc)";

a copolymer of resins [ K3] (Ba) and (Bc);

a resin [ K4] obtained by reacting a copolymer of (Ba) and (Bc) with (Bb);

a resin [ K5] obtained by reacting a copolymer of (Bb) and (Bc) with (Ba);

the resin [ K6] is a resin obtained by reacting a copolymer of (Bb) and (Bc) with (Ba) and further with a carboxylic acid anhydride.

Specific examples of (Ba) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid;

carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Unsaturated dicarboxylic anhydrides such as 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] hept-2-ene anhydride;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [ 2- (meth) acryloyloxyethyl ] ester;

and unsaturated (meth) acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.

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

(Bb) is a polymerizable compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. The (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid. The same applies to "(meth) acryloyl group" and "(meth) acrylate" and the like.

Examples of (Bb) include a monomer having an epoxyethyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond, and the like.

The (Bb) is preferably a monomer having an ethylene oxide group and an ethylenically unsaturated bond, in view of enabling the color filter to have higher reliability such as heat resistance and chemical resistance.

Examples of (Bc) include 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, and propyl (meth) acrylate2-methylcyclohexyl alkenoate, tricyclo [5.2.1.0 ] meth (acrylate)^2,6]Decan-8-yl ester (commonly known in the art as "dicyclopentyl (meth) acrylate". Alter, tricyclodecanyl (meth) acrylate ") and tricyclo [5.2.1.0 ^2,6]Decen-8-yl (meth) acrylate (referred to as "dicyclopentenyl (meth) acrylate" as a common name in the art), dicyclopentenyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, and other (meth) acrylate esters;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [ 2.1] hept-2-ene, 5, 6-bis (2.1) hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxyhept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-2.1 ] hept-2, Bicyclic unsaturated compounds such as 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

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

styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like.

Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

Specific examples of the resin (B) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer and a 3, 4-epoxytricyclo [5.2.1.0 ] ^2.6]Resins such as decyl acrylate/(meth) acrylic acid copolymers [ K1 ]](ii) a Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ]^2.6]Decyl acrylate/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxytricyclo [5.2.1.0^2.6]Resins such as decyl acrylate/(meth) acrylic acid/N-cyclohexylmaleimide copolymer/hydroxyl group-containing (meth) acrylate copolymer and 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer [ K2 ]](ii) a Resins [ K3 ] such as benzyl (meth) acrylate/(meth) acrylic acid copolymer and styrene/(meth) acrylic acid copolymer](ii) a A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate/(meth) acrylic acid copolymer, and a resin obtained by adding tricyclodecanyl (meth) acrylate/styrene/(meth) acrylic acid copolymerResins such as glycidyl (meth) acrylate resins and resins obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate/benzyl (meth) acrylate/meth) acrylic acid copolymer [ K4 ](ii) a Resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) with (meth) acrylic acid, and resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/styrene/(glycidyl (meth) acrylate) with (meth) acrylic acid [ K5](ii) a Resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) with (meth) acrylic acid and further reacting the resulting resin with tetrahydrophthalic anhydride [ K6 ]]And the like.

Among them, as the resin (B), the resin [ K1] and the resin [ K2] are preferable.

For example, the resin [ K1] can be produced by a method described in "Experimental method for Polymer Synthesis" (published by Otsuka institute of Engineers, 1 st edition, 1 st 1972, 3.1.1) and a cited reference described in the above document.

The copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a solid (powder) taken out by a method such as reprecipitation. In particular, in the polymerization, by using the solvent contained in the coloring composition of the present invention as a solvent, the solution after the reaction can be used as it is for preparing the coloring composition of the present invention, and therefore, the production process of the coloring composition of the present invention can be simplified.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. When the molecular weight is within the above range, the color filter tends to have high hardness, a high residual film ratio, good solubility in a developer of unexposed portions, and high resolution of a colored pattern.

The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150, and still more preferably 70 to 135 mg-KOH/g. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be determined by titration with an aqueous solution of potassium hydroxide, for example.

The content of the resin (B) is preferably 10 to 90 parts by mass, more preferably 20 to 85 parts by mass, and still more preferably 30 to 80 parts by mass, based on 100 parts by mass of the solid content. If the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the residual film ratio of the colored pattern tend to be improved.

(solvent (E))

The solvent (E) that can be contained in the coloring composition is not particularly limited, and 2 or more solvents that are generally used in this field may be used alone or in combination. Examples thereof include ester solvents (solvents containing-COO-and not-O-in the molecule), ether solvents (solvents containing-O-and not-COO-in the molecule), ether ester solvents (solvents containing-COO-and not-O-in the molecule), ketone solvents (solvents containing-CO-and not-COO-in the molecule), alcohol solvents (solvents containing OH and not-O-, -CO-, and-COO-, in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, 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, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-dibutylene glycolAlkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.

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

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.

The solvent is preferably 1 solvent selected from propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, N-dimethylformamide, and tetrahydrofuran, or a mixed solvent combining 2 or more, and more preferably 1 solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, N-methylpyrrolidone, N-dimethylformamide, and tetrahydrofuran, or a mixed solvent combining 2 or more.

The content of the solvent (E) is preferably 70 to 95 parts by mass, and more preferably 75 to 92 parts by mass, per 100 parts by mass of the coloring composition of the present invention. In other words, the total amount of the solid components in the coloring composition is preferably 5 to 30 parts by mass, and more preferably 8 to 25 parts by mass. If the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is not insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

(leveling agent (F))

Examples of the leveling agent (F) that can be contained in the coloring composition include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Toray Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance materials Japan Co., Ltd.) may be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F183, MEGAFACE F554, MEGAFACE R30, MEGAFACE RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Material electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nitro Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemicals Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFACE (registered trademark) R08, MEGAFACE BL20, MEGAFACEF475, MEGAFACE F477, and MEGAFACE F443 (manufactured by DIC corporation) and the like can be mentioned.

The content of the leveling agent (F) is preferably 0.0001 to 0.2 parts by mass, more preferably 0.0002 to 0.1 parts by mass, and still more preferably 0.0003 to 0.05 parts by mass, based on 100 parts by mass of the coloring composition. Note that this content does not include the content of the pigment dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

(other Components of the coloring composition)

The coloring composition may contain additives known in the art, such as a filler, another polymer compound, an adhesion promoter, an antioxidant, and a light stabilizer, as required.

(method for producing coloring composition)

The coloring composition can be prepared, for example, by mixing the colorant (a), the resin (B), the solvent (E), and the leveling agent (F) together with other components as needed.

The pigment (A2) is preferably mixed with a part or all of the solvent (E) in advance, and dispersed by a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. The pigment dispersion thus obtained can be mixed with the remaining components to a predetermined concentration to prepare a desired coloring composition.

The dyes may be dissolved in a part or all of the solvent (E) separately in advance to prepare a solution. Preferably, the solution is filtered through a filter having a pore size of about 0.01 to 1 μm.

The mixed coloring composition is preferably filtered through a filter having a pore size of about 0.1 to 10 μm.

(colored curable resin composition)

The colored curable resin composition of the present invention comprises the above colored composition, a polymerizable compound (C), and a polymerization initiator (D). The colored curable resin composition may further contain a polymerization initiator (D1).

The colored curable resin composition of the present invention can be expected to have an excellent absorbance retention rate before and after the light resistance test. The colored curable resin composition is expected to have excellent heat resistance.

(polymerizable Compound (C))

The polymerizable compound (C) contained in the colored curable resin composition is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and preferably (meth) acrylate compounds.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include compounds having 1 ethylenically unsaturated bond such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the compounds exemplified as (Ba), (Bb), and (Bc) above;

compounds having 2 ethylenically unsaturated bonds such as 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate;

Compounds having 3 ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and the like;

compounds having 4 ethylenically unsaturated bonds such as pentaerythritol tetra (meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified pentaerythritol tetra (meth) acrylate;

compounds having 5 ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;

compounds having 6 ethylenically unsaturated bonds such as dipentaerythritol hexa (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate;

compounds having 7 or more ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, and tetrapentaerythritol deca (meth) acrylate; and the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2900, more preferably 250 to 1500.

The content of the polymerizable compound (C) is preferably 7 to 65 parts by mass, more preferably 13 to 60 parts by mass, and still more preferably 17 to 55 parts by mass, per 100 parts by mass of the solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

The content ratio of the resin (B) to the polymerizable compound (C) [ resin (B): polymerizable compound (C) ] is preferably 20:80 to 80:20, and more preferably 35:65 to 80:20 on a mass basis.

(polymerization initiator (D))

The polymerization initiator (D) contained in the colored curable resin composition is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. As the polymerization initiator generating active radicals, for example, an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a bisimidazole compound can be cited.

The O-acyloxime compound is a compound having a partial structure represented by the formula (Dd 1). Hereinafter, the bonding site is denoted.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylthiophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, and the like. Commercially available products such as IRGACURE (registered trademark) OXE01, OXE02 (both of which are manufactured by BASF corporation), N-1919 (manufactured by ADEKA corporation) and the like can be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylthiophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine. These O-acyloxime compounds tend to give color filters of high brightness.

The alkylphenone compound is a compound having a partial structure represented by the following formula (Dd2) or a partial structure represented by the following formula (Dd 3). In the partial structure of these, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (Dd2) include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholino) phenyl ] butan-1-one. Commercially available products such as IRGACURE 369, 907, and 379 (all of which are manufactured by BASF) can be used.

Examples of the compound having a partial structure represented by the formula (Dd3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, and benzildimethylketal.

In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (Dd 2).

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1, 3, 5-triazine, 2, 4-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-methylfuran-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine and the like.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as IRGACURE (registered trademark) 819 (manufactured by BASF) can be used.

Examples of the bisimidazole compound include compounds represented by the following formula (Dd 4).

[ in the formula (Dd4), R^d1～R^d5Represents an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

In the formula (Dd4), R is^d1～R^d5Examples of the aryl group having 6 to 10 carbon atoms in (A) include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group and a naphthyl group, and a phenyl group is preferable.

Examples of the substituent that the aryl group having 6 to 10 carbon atoms may have include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include R in the formula (I)¹～R⁴The halogen atom exemplified in (1). Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and a methoxy group is preferable.

Specific examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl biimidazole, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenyl biimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carbonylalkoxy group (see, for example, JP-A-7-10913). Among them, compounds represented by the following formula and mixtures thereof are preferable.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) described later.

Examples of the polymerization initiator generating an acid include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate and benzoin tosylate.

As the polymerization initiator (D), a polymerization initiator that generates an active radical is preferable, a polymerization initiator containing at least 1 selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole compound is more preferable, and a polymerization initiator containing an O-acyloxime compound is further preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be shortened, so that the productivity of the color filter tends to be improved.

(polymerization initiation assistant (D1))

The polymerization initiator aid (D1) that can be contained in the colored curable resin composition is a compound or sensitizer for promoting the polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like; aminobenzoic acid esters such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 2-ethylhexyl 4-dimethylaminobenzoate; alkylaminobenzophenones such as N, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (known as michler's ketone), 4 '-bis (diethylamino) benzophenone, and 4, 4' -bis (ethylmethylamino) benzophenone; and the like, among them, alkylaminobenzophenones are preferable, and 4, 4' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical industries, Ltd.) can be used.

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, and 2-ethyl-9, 10-dibutoxyanthracene.

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

Examples of the carboxylic acid compound include phenylthioglycolic acid, methylphenylthioacetic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylthioacetic acid, methoxyphenylthioglycolic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioglycolic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

When the polymerization initiator aid (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.

(other Components in the colored curable resin composition)

The colored curable resin composition may contain, if necessary, additives known in the art, such as a chain transfer agent.

(method for producing colored curable resin composition)

The colored curable resin composition can be prepared, for example, by mixing the colored composition with the polymerizable compound (C), the polymerization initiator (D), the polymerization initiation aid (D1), and other components. The colored curable resin composition is preferably used in the case of patterning by photolithography. The mixed colored curable resin composition is preferably filtered through a filter having a pore size of about 0.1 to 10 μm.

(color Filter and method for producing the same)

The color filter of the present invention may be formed of the colored composition or the colored curable resin composition described above. The color filter of the present invention is excellent in the absorbance retention before and after the light resistance test. The color filter is also excellent in heat resistance.

Examples of a method for producing a color filter formed of a colored composition or a colored curable resin composition include a method in which a substrate is coated with a colored composition or a colored curable resin composition, and dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and dry the composition to form a smooth composition layer, followed by postbaking. The cured coating film thus formed may be a color filter of the present invention.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass coated with silica on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, or a substrate such as silicon, or a substrate in which an aluminum, silver/copper/palladium alloy thin film is formed on the above substrate, is used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Examples of the coating method include spin coating, slit coating, and slit spin coating.

The temperature for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

The thickness of the composition layer formed by applying the colored composition or the colored curable resin composition is not particularly limited, and may be appropriately selected depending on the film thickness of the color filter to be targeted.

The resulting composition layer is preferably further subjected to post-baking. The post-baking temperature is preferably 150 to 250 ℃, and more preferably 160 to 235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

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

The cured coating film thus obtained may be patterned by, for example, etching.

The colored pattern can also be produced by photolithography, an ink jet method, a printing method, or the like using the colored composition or the colored curable resin composition of the present invention. Among them, when a colored curable resin composition containing a polymerizable compound (C) and a polymerization initiator (D) is used, photolithography is preferable. The photolithography method is a method in which a colored curable resin composition is applied to a substrate, dried to form a composition layer, and the composition layer is exposed to light through a photomask and developed. The coating and drying can be carried out under the above conditions.

The composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use is used.

As the light source for exposure, a light source generating light having a wavelength of 250 to 450nm is preferable. For example, the light having a wavelength lower than 350nm may be cut off by using a filter for cutting off the wavelength region, or the light having a wavelength around 436nm, 408nm, or 365nm may be selectively extracted by using a band-pass filter for extracting the wavelength region. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be given.

Since parallel light can be uniformly irradiated to the entire exposure surface or accurate alignment of the photomask and the substrate on which the composition layer is formed can be performed, an exposure apparatus such as a mask aligner and a stepper is preferably used.

The exposed composition layer is developed by contacting it with a developing solution, thereby forming a colored pattern on the substrate. The unexposed portion of the composition layer is dissolved in a developing solution and removed by development. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of a spin-on immersion (dip) method, a dipping method, a spraying method, and the like. Further, the substrate may be inclined at an arbitrary angle at the time of development.

It is preferable to carry out water washing after development.

The resulting colored pattern is preferably post-baked. The post-bake temperature and time may be the same as those described above.

The color filter is preferably used for a solid-state imaging element and a display device (e.g., a liquid crystal display device, an organic EL device, electronic paper, etc.).

(optical Filter)

The compound (I) can be used, for example, for an optical filter of a display device or the like. The optical filter can be expected to have an excellent absorbance retention ratio before and after the light resistance test. It is also expected that the optical filter has excellent heat resistance.

The optical filter is generally a layer formed from a composition containing a light-transmitting (preferably optically transparent) thermoplastic resin or thermosetting resin, and may be a film-like material, for example. The optical filter may be a color correction film having a single-layer structure of the color correction layer or a laminate having a multilayer structure including the color correction layer, as long as the optical filter has a layer containing the compound (I) (hereinafter, may be referred to as "color correction layer"). When the optical filter has a multilayer structure, 1 color correction layer may be included, or 2 or more color correction layers may be included, and the compounds (I) contained in the 2 or more layers may be the same or different from each other.

When the optical filter is a laminate, the color correction layer may be an adhesive layer or a resin layer other than the adhesive layer (hereinafter, may be simply referred to as "resin layer"). When the color correction layer is an adhesive layer, 2 layers included in the optical filter may be bonded to each other, or the optical filter may be used to bond other members such as an image display element. The adhesive layer may be an adhesive layer formed of an adhesive or an adhesive layer formed of an adhesive.

When the color correction layer is an optical filter (color correction film) having a single-layer structure or when the optical filter having a multilayer structure is a resin layer other than the adhesive layer, the method of containing the compound (I) in the color correction film or the resin layer is not particularly limited. For example, a method of kneading with a resin for forming a color correction film or a resin layer and heating and molding into a film shape; [ ii ] A method of forming a color correction film or a resin layer by dispersing or dissolving a resin or a monomer of the resin and a compound (I) in an organic solvent and molding the solution into a film shape by a casting method or the like. Further, [ iii ] the resin layer may be formed by applying a coating liquid in which the compound (I) is dispersed or dissolved in a binder resin or an organic solvent to a resin base film, or a film obtained by peeling the resin base film from the resin layer may be used as a color correction film. The thickness of the color correction film or the resin layer is not particularly limited, and may be, for example, 1 μm to 200 μm.

When the color correction film or the resin layer contains the compound (I), the content thereof is not particularly limited. For example, the amount of the compound (I) may be 0.001 part by mass or more, preferably 0.02 part by mass or more, more preferably 0.05 part by mass or more, and may be 10 parts by mass or less, preferably 3 parts by mass or less, more preferably 0.5 part by mass or less, based on 100 parts by mass of the base polymer forming the color correction film or the resin layer.

When the color correction layer is an adhesive layer, a method for containing the compound (I) in the adhesive layer is not particularly limited, and the compound (I) may be added when preparing an adhesive composition or a binder composition for forming the adhesive layer. The thickness of the adhesive layer is not particularly limited, and may be, for example, 1 μm to 100 μm.

When the adhesive layer contains the compound (I), the content thereof is also not particularly limited. For example, the amount of the compound (I) may be 0.01 part by mass or more, preferably 0.02 part by mass or more, more preferably 0.05 part by mass or more, and may be 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 0.5 part by mass or less, per 100 parts by mass of the base polymer forming the binder and/or the binder contained in the adhesive layer.

The optical filter can be used in a display device such as an organic electroluminescence (organic EL) display device or a liquid crystal display device, and can be used by being attached to a visible side of an image display element of the display device. In this case, the optical filter preferably has an adhesive layer and a resin layer other than the adhesive layer, and at least one of the adhesive layer and the resin layer is preferably a color correction layer containing the compound (I).

When the optical filter is a laminate, the laminate structure thereof is not particularly limited, and for example, the optical filter may have a laminate structure shown in fig. 1 (a) and (b). Fig. 1 (a) and (b) are schematic cross-sectional views showing an example of an optical filter. The optical filter 10 shown in fig. 1 (a) can be used for an organic EL display device. The optical filter 10 may include, for example, an image display element pressure-sensitive adhesive layer 11, a phase difference film 12, a pressure-sensitive adhesive layer 13, a 1 st protective film 14, a polarizing film 15, and a 2 nd protective film 16 in this order. The pressure-sensitive adhesive layer 11 and the pressure-sensitive adhesive layer 13 for the image display element correspond to the above-mentioned adhesive layers, and the retardation film 12, the 1 st protective film 14, the polarizing film 15, and the 2 nd protective film 16 correspond to the above-mentioned resin layers.

The 1 st protective film 14, the polarizing film 15, and the 2 nd protective film 16 in the optical filter 10 form a polarizing plate, and the 1 st protective film 14 and the 2 nd protective film 16 may have an adhesive layer on the side of the lamination surface with the polarizing film 15. The pressure-sensitive adhesive layer 11 for an image display element is used for bonding to a light-emitting layer of an organic EL element including an image display element of an organic EL display device. A not-shown spacer (release film) may be provided on the surface of the image display element pressure-sensitive adhesive layer 11 opposite to the phase difference film 12.

The optical filter 20 shown in fig. 1 (b) can be used for a liquid crystal display device. The optical filter 20 may include, for example, an image display element adhesive layer 21, a 1 st protective film 24, a polarizing film 25, and a 2 nd protective film 26 in this order. The image display element pressure-sensitive adhesive layer 21 corresponds to the above adhesive layer, and the 1 st protective film 24, the polarizing film 25, and the 2 nd protective film 26 all correspond to the above resin layer.

The 1 st protective film 24, the polarizing film 25, and the 2 nd protective film 26 in the optical filter 20 form polarizing plates, and the 1 st protective film 24 and the 2 nd protective film 26 may have an adhesive layer on the side of the lamination surface with the polarizing film 25. The pressure-sensitive adhesive layer 21 for an image display element is used for bonding to a liquid crystal cell as an image display element of a liquid crystal display device. A spacer (release film), not shown, may be provided on the surface of the image display element pressure-sensitive adhesive layer 21 opposite to the 1 st protective film 24.

The compound (I) may be contained in at least either one of the resin layer and the adhesive layer forming the optical filters 10 and 20 shown in (a) and (b) in fig. 1. In the optical filter 10 shown in fig. 1 (a), the compound (I) may be contained in 1 or more of the pressure-sensitive adhesive layer 11, the pressure-sensitive adhesive layer 13, the 1 st protective film 14, and the 2 nd protective film 16 for an image display element, for example. In the optical filter 20 shown in fig. 1 (b), the compound (I) may be contained in 1 or more of the pressure-sensitive adhesive layer 21 for an image display element, the 1 st protective film 24, and the 2 nd protective film 26, for example.

The optical filters 10 and 20 shown in fig. 1 (a) and (b) are merely examples, and may have a laminated structure other than the above. For example, the 2 nd protective films 16 and 26 may have other layers such as a film having an antiglare function and a film having a surface antireflection function on the surfaces opposite to the polarizing films 15 and 25. The 1 st protective films 14 and 24 may have a function as retardation films, and the 2 nd protective films 16 and 26 may have an antiglare function, a surface antireflection function, a function as retardation films, and the like. Further, in addition to the layers forming the optical filters 10 and 20 shown in (a) and (b) in fig. 1, a color correction layer containing the compound (I) may be provided at an arbitrary position.

Since the optical filter contains the compound (I), it can be expected to have an excellent absorbance retention rate before and after the light resistance test. The optical filter can be expected to have excellent heat resistance.

Hereinafter, each member constituting the optical filter will be described in detail.

(adhesive layer)

Examples of the adhesive that can be used for the adhesive layer include an aqueous adhesive, an active energy ray-curable adhesive, and a combination thereof. Examples of the aqueous adhesive include a polyvinyl alcohol resin aqueous solution and an aqueous two-pack polyurethane emulsion adhesive. The active energy ray-curable adhesive is an adhesive that is cured by irradiation with an active energy ray such as ultraviolet ray, and examples thereof include an adhesive containing a polymerizable compound and a photopolymerization initiator, an adhesive containing a photoreactive resin, and an adhesive containing a binder resin and a photoreactive crosslinking agent. Examples of the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable (meth) acrylic monomer, and a photocurable polyurethane monomer, and oligomers derived from these monomers. Examples of the photopolymerization initiator include photopolymerization initiators containing active species that generate neutral radicals, anionic radicals, and cationic radicals by irradiation with active energy rays such as ultraviolet rays.

As the adhesive usable for the adhesive layer, a conventionally known adhesive can be used. Examples of the adhesive include a (meth) acrylic adhesive, a urethane adhesive, a silicone adhesive, a polyester adhesive, a polyamide adhesive, a polyether adhesive, a fluorine adhesive, and a rubber adhesive. Further, an energy ray-curable adhesive, a thermosetting adhesive, or the like may be used. Among them, a (meth) acrylic adhesive is preferably used from the viewpoint of transparency, adhesion, reliability, and the like.

The (meth) acrylic pressure-sensitive adhesive is not particularly limited, and the polymer containing (50 mass% or more) of (meth) acrylic acid ester as a main component may be a homopolymer of 1 kind of (meth) acrylic acid ester, or a copolymer of (meth) acrylic acid ester with another (meth) acrylic acid ester or the like. Examples of the (meth) acrylic acid ester include butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2-phenoxyethyl (meth) acrylate. In addition, a polar monomer may be copolymerized in the polymer mainly composed of the (meth) acrylate. Examples of the polar monomer include monomers having a polar functional group such as a carboxyl group, a hydroxyl group, an amide group, an amino group, and an epoxy group, such as (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, 2- (N, N-dimethylamino) ethyl (meth) acrylate, and glycidyl (meth) acrylate. The (meth) acrylic resin used in the (meth) acrylic adhesive may be a (meth) acrylic resin having a weight average molecular weight (Mw) of 10 ten thousand or more, preferably 60 ten thousand or more, and usually 250 ten thousand or less.

These (meth) acrylic adhesives may be used alone, and are usually used in combination with a crosslinking agent. Examples of the crosslinking agent include: a 2-valent or polyvalent metal ion which is a substance that forms a metal salt of a carboxylic acid with a carboxyl group, an amine compound which is a substance that forms an amide bond with a carboxyl group, an epoxy compound or a diol compound which is a substance that forms an ester bond with a carboxyl group, an isocyanate compound which is a substance that forms an amide bond with a carboxyl group, and the like. Among them, isocyanate compounds are preferably used.

Among the isocyanate-based compounds, m-xylylene diisocyanate, toluene diisocyanate, or hexamethylene diisocyanate is preferably used; adducts obtained by reacting polyols such as glycerin and trimethylolpropane with these isocyanate compounds; a substance which forms a dimer, trimer or the like of these isocyanate compounds or a mixture thereof; mixtures of 2 or more of the above-mentioned isocyanate compounds, and the like.

Preferred examples of the isocyanate compound include toluene diisocyanate, an adduct obtained by reacting a polyol with toluene diisocyanate, a dimer of toluene diisocyanate, a trimer of toluene diisocyanate, hexamethylene diisocyanate, an adduct obtained by reacting a polyol with hexamethylene diisocyanate, a dimer of hexamethylene diisocyanate, and a trimer of hexamethylene diisocyanate.

The content of the crosslinking agent in the acrylic adhesive is usually 0 to 5 parts by mass, preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the (meth) acrylic resin.

The acrylic adhesive may further contain a silane compound. When the acrylic pressure-sensitive adhesive contains a silane compound, the adhesion between the obtained pressure-sensitive adhesive layer and an optical member such as a glass substrate can be improved.

Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane. More than 2 silane compounds may be used.

The silane compound may be a silicone oligomer type silane compound. When the silicone oligomer is expressed as a (monomeric) oligomer, examples thereof include a 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, a mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, a 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, a 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, a 3-acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, a vinyltrimethoxysilane-tetramethoxysilane copolymer, and the like.

The content of the silane compound in the adhesive composition is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the (meth) acrylic resin. When the content of the silane compound is 0.01 parts by mass or more, the effect of improving the adhesion between the pressure-sensitive adhesive layer and the optical member such as the glass substrate can be easily obtained. Further, if the content of the silane compound is 10 parts by mass or less, bleeding of the silane compound from the pressure-sensitive adhesive layer can be suppressed.

The acrylic adhesive may further contain an ionic compound as an antistatic agent for imparting antistatic properties. The ionic compound is a compound having an inorganic cation or an organic cation and an inorganic anion or an organic anion. The acrylic adhesive may contain 2 or more kinds of ionic compounds.

Examples of the inorganic cation include lithium cation [ Li ]⁺Sodium cation [ Na ]⁺Potassium cation [ K ]⁺Alkali metal ion, beryllium cation [ Be ]²⁺Magnesium cation [ Mg ]²⁺Calcium cation [ Ca ]²⁺Alkaline earth metal ions, etc.

Examples of the organic cation include an imidazolium cation, a pyridinium cation, a pyrrolidinium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation.

Examples of the inorganic anion include chloride ion [ Cl ]^－Bromine ion [ Br ]^－Oxygen ion [ I ]^－Tetrachloroaluminate anion [ AlCl ]₄ ^－Heptachlorodialuminate anion [ Al ]₂Cl₇ ^－Tetrafluoroborate anion [ BF ]₄ ^－Hexafluorophosphate anion [ PF ]₆ ^－Perchlorate anion [ ClO ]₄ ^－Nitrate anion [ NO ]₃ ^－Hexafluoroarsenate anion [ AsF ]₆ ^－Hexafluoroantimonate anion [ SbF ] ₆ ^－Hexafluoroniobate anion [ NbF ]₆ ^－Hexafluorotantalate anion [ TaF ]₆ ^－Dicyandiamide anion [ (CN)₂N^－And the like.

As the organic anion, for example, acetate anion [ CH ] can be mentioned₃COO^－Trifluoroacetate anion [ CF ]₃COO^－Methanesulfonate anion [ CH ]₃SO₃ ^－Triflate anion [ CF ]₃SO₃ ^－P-toluenesulfonate anion [ p-CH ]₃C₆H₄SO₃ ^－Bis (fluorosulfonyl) imide anion [ (FSO)₂)₂N- ], bis (trifluoromethanesulfonyl) imide anion [ (CF)₃SO₂)₂N- ], tris (trifluoromethanesulfonyl) methylate anion [ (CF)₃SO₂)₃C- ], dimethylphosphinate anion [ (CH)₃)₂POO- ], (poly) hydrofluorofluoride anions [ F (HF)_n- (n is about 1 to 3), thiocyanate anion [ SCN- ], perfluorobutaneSulfonate anion [ C₄F₉SO₃- ], bis (pentafluoroethanesulfonyl) imide anion [ (C)₂F₅SO₂)₂N^－Perfluorobutyrate anion [ C ]₃F₇COO^－(trifluoromethanesulfonyl) imide anion [ (CF)₃SO₂)(CF₃CO)N^－And the like.

Specific examples of the ionic compound can be selected from the combinations of the above-mentioned cationic components and anionic components.

Examples of the ionic compound having an organic cation include pyridinium salts such as N-octylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-butyl-4-methylpyridinium hexafluorophosphate, N-decylpyridinium bis (fluorosulfonyl) imide salt, N-hexylpyridinium bis (trifluoromethanesulfonyl) imide salt, and N-octylpyridinium bis (trifluoromethanesulfonyl) imide salt, imidazolium salts such as 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide salt, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, and 1-butyl-3-methylimidazolium methanesulfonate salt; pyrrolidinium salts such as N-butyl-N-methylpyrrolidinium hexafluorophosphate, N-butyl-N-methylpyrrolidinium bis (fluorosulfonyl) imide salt, and N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt; quaternary ammonium salts such as tetrabutylammonium hexafluorophosphate and tetrabutylammonium p-toluenesulfonate.

Examples of the ionic compound having an inorganic cation include lithium bromide, lithium iodide, and sodium hexafluorophosphate.

From the viewpoint of maintaining antistatic properties, the ionic compound is preferably solid at room temperature. The ionic compound preferably has a melting point of 30 ℃ or higher, and further 35 ℃ or higher. On the other hand, if the melting point is too high, the compatibility with the (meth) acrylic resin deteriorates, and therefore the melting point of the ionic compound is preferably 90 ℃ or less, more preferably 70 ℃ or less, and still more preferably less than 50 ℃.

The content of the ionic compound in the acrylic adhesive is preferably 0.1 to 8 parts by mass, more preferably 0.2 to 6 parts by mass, further preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 5 parts by mass, based on 100 parts by mass of the (meth) acrylic resin. The content of the ionic compound is 0.1 part by mass or more, which is advantageous for improving antistatic performance, and 8 parts by mass or less, which is advantageous for maintaining durability of the pressure-sensitive adhesive layer.

Various additives may be further blended in the adhesive or the pressure-sensitive adhesive. Examples of the additives include a reworking agent, a tackiness imparting resin, an antioxidant, an ultraviolet absorber, an antifoaming agent, a corrosive agent, and a light diffusing agent such as fine particles.

(resin layer)

Examples of the resin layer include a polarizing film as a linear polarizer; a protective film provided for protecting the surface of the polarizing film or the like; a phase difference film; an optical compensation film other than the retardation film; a film having an antiglare function and a film having a surface antireflection function, each of which has a concavo-convex shape on the surface; a reflective film having a reflective function on a surface thereof; a semi-transmissive reflective film having both a reflective function and a transmissive function; a light diffusion film; hard coating; color correction films, and the like. The optical filter may include 1 or 2 or more of the above resin layers.

Examples of the polarizing film include a polarizing film in which iodine is oriented in a polyvinyl alcohol resin layer, a polarizing film in which a liquid crystal compound and a dichroic dye are oriented, and the like.

The resin layer is not particularly limited as a material other than the polarizing film, and examples thereof include polyolefin resins such as chain polyolefin resins (polyethylene resins, polypropylene resins, and the like) and cyclic polyolefin resins (norbornene resins, and the like); cellulose ester resins such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; a polycarbonate-based resin; (meth) acrylic resins such as (meth) acrylic acid and polymethyl (meth) acrylate; vinyl alcohol resins such as polyvinyl alcohol and polyvinyl acetate; a polystyrene-based resin; mixtures, copolymers, etc. of these. These resins may contain 1 or 2 or more kinds of additives such as lubricants, plasticizers, dispersants, heat stabilizers, ultraviolet absorbers, infrared absorbers, antistatic agents, antioxidants, light diffusers such as fine particles, and the like.

(display device)

The color filter and the optical filter can be preferably used for display devices such as organic EL display devices, liquid crystal display devices, inorganic electroluminescence (inorganic EL) display devices, electron emission display devices, and electronic paper.

Fig. 2 (a) and (b) are schematic cross-sectional views showing an example of a display device including an optical filter. The display device shown in fig. 2 (a) is an organic EL display device including the optical filter 10 shown in fig. 1 (a) and the image display element 1 as a light emitting layer including an organic EL element. The optical filter 10 may be disposed on the visible side of the image display element 1 via the adhesive layer 11 for image display element.

The display device shown in fig. 2 (b) is a liquid crystal display device including the optical filter 20 shown in fig. 1 (b) and the image display element 2 as a liquid crystal cell including a liquid crystal layer. The optical filter 20 may be disposed on the visible side of the image display element 2 via the adhesive layer 21 for image display element.

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Compound and coloring composition

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