JP7634353B2 - Colored curable resin composition - Google Patents

Description

The present invention relates to a colored curable resin composition.

Color filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors, are manufactured from colored curable resin compositions. One such colored curable resin composition known is one that contains only a xanthene compound represented by the following formula as a colorant (Patent Document 1).

JP 2016-27075 A

Conventionally known color filters formed from the above-mentioned colored curable resin compositions do not have fully satisfactory light resistance.

［式（Ａ１）中、
Ａ¹及びＡ²は、それぞれ独立に、置換基を有していてもよいフェニレン基を表す。
Ｌ¹及びＬ²は、それぞれ独立に、炭素数１～１５の２価の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－ＳＯ₂－又は―ＮＲ⁷―に置き換わっていてもよい。ただし、隣接する－ＣＨ₂－が同時に同種の基に置換されることはない。
Ｒ¹～Ｒ⁶は、それぞれ独立に、水素原子、ハロゲン原子又は炭素数１～８のアルキル基を表す。
Ｒ⁷は、水素原子又は炭素数１～８のアルキル基を表す。］

［式（Ａ２）中、Ｒ²¹～Ｒ²⁴は、互いに独立に、水素原子、置換基（ただし、－ＣＯ₂Ｈ
を除く）を有していてもよい炭素数１～２０の１価の炭化水素基又は－Ｒ⁵⁰－Ｓｉ（Ｒ²⁹）₃を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－ＣＯ－又は－ＮＲ³⁰－で置き換わっていてもよい。ただし、隣接する－ＣＨ₂－が同時に同種の基に置換されることはない。Ｒ²¹及びＲ²²は、一緒になって窒素原子を含む環を形成してもよく、Ｒ²³及びＲ²⁴は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ²⁵は、－ＯＨ、－ＳＯ₃ ^-、－ＳＯ₃Ｈ、－ＳＯ₃ ^-Ｚ⁺、－ＣＯ₂ ^-、－ＣＯ₂Ｈ、－ＣＯ₂ ^-Ｚ⁺、－ＣＯ₂Ｒ²⁸、－ＳＯ₃Ｒ²⁸又は－Ｒ⁵⁰－Ｓｉ（Ｒ²⁹）₃を表す。
Ｒ²⁶及びＲ²⁷は、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。
ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ²⁵は同一でも異なってもよい。
ａは、０又は１を表す。
Ｘ^-は、任意のアニオンを表す。
Ｚ⁺は、任意のカチオンを表す。
Ｒ²⁸は、炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。Ｒ²⁸が複数存在する場合、複数のＲ²⁸は、それぞれ同一であっても異なっていてもよい。
Ｒ⁵⁰は、炭素数１～１０のアルカンジイル基を表し、該アルカンジイル基を構成する－ＣＨ₂－は、－Ｏ－、－ＣＯ－、－ＮＲ³⁰－、－ＯＣＯ－、－ＣＯＯ－、－ＯＣＯＮＨ－、－ＣＯＮＨ－又は－ＮＨＣＯ－で置き換わっていてもよい。ただし、隣接する－ＣＨ₂－が同時に同種の基に置換されることはない。
Ｒ²⁹は、水素原子、ヒドロキシ基、炭素数１～４のアルキル基又は炭素数１～４のアルコキシ基を表し、複数のＲ²⁹は、それぞれ同一であっても異なっていてもよい。
Ｒ³⁰は、水素原子又は炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。］
［２］ ［１］記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［３］ ［２］記載のカラーフィルタを含む表示装置。 The gist of the present invention is as follows.
[1] A composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator,
A colored curable resin composition, comprising a colorant comprising a compound represented by formula (A1) and a compound represented by formula (A2).

[In formula (A1),
A ¹ and A ² each independently represent a phenylene group which may have a substituent.
^L1 and ^L2 each independently represent a divalent hydrocarbon group having 1 to 15 carbon atoms, and _-CH2- contained in the hydrocarbon group may be replaced by -O-, _-SO2- or ^-NR7- , provided that adjacent _-CH2- are not simultaneously replaced by the same type of group.
R ¹ to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In formula (A2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a substituent (including -CO ₂ H
or ^-R50 -Si( ^R29 ) ₃ , where _-CH2- contained in the hydrocarbon group may be replaced by -O-, -CO- or ^-NR30- , provided that adjacent _-CH2- are not simultaneously replaced by the same type of group. ^R21 and R22 may be joined together to form a ring containing a nitrogen atom, and ^{R23 and R24} may be joined together to form a ring containing a nitrogen atom.
R ²⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ ^- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ²⁸ , -SO ₃ R ²⁸ or -R ⁵⁰ -Si(R ²⁹ ) ₃ .
R ²⁶ and R ²⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, multiple R ²⁵ may be the same or different.
a represents 0 or 1.
X ⁻ represents any anion.
Z ⁺ represents any cation.
R ²⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. When a plurality of R ^28s are present, the plurality of R ^28s may be the same or different.
R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and --CH ₂ -- constituting the alkanediyl group may be replaced by --O--, --CO--, --NR ³⁰ --, --OCO--, --COO--, --OCONH--, --CONH-- or --NHCO--, provided that adjacent --CH ₂ --s are not simultaneously replaced by the same type of group.
R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and multiple R ^29s may be the same or different.
R ³⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
[2] A color filter formed from the colored curable resin composition according to [1].
[3] A display device comprising the color filter according to [2].

The colored curable resin composition of the present invention can form a color filter with excellent light resistance.

<Colored curable resin composition>
The colored curable resin composition of the present invention contains a colorant (hereinafter, may be referred to as "colorant (A)"), a resin (hereinafter, may be referred to as "resin (B)"), a polymerizable compound (hereinafter, may be referred to as "polymerizable compound (C)"), and a polymerization initiator (hereinafter, may be referred to as "polymerization initiator (D)"). In this specification, the compounds exemplified as each component may be used alone or in combination, unless otherwise specified.

<Colorant (A)>
The colorant (A) contains a compound represented by formula (A1) (hereinafter, may be referred to as “compound (A1)”) and a compound represented by formula (A2) (hereinafter, may be referred to as “compound (A2)”).

Compound (A1) is as follows:

[In formula (A1),
A ¹ and A ² each independently represent a phenylene group which may have a substituent.
^L1 and ^L2 each independently represent a divalent hydrocarbon group having 1 to 15 carbon atoms, and _-CH2- contained in the hydrocarbon group may be replaced by -O-, _-SO2- or ^-NR7- , provided that adjacent _-CH2- are not simultaneously replaced by the same type of group.
R ¹ to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Examples of the substituent that the phenylene group represented by ^A1 and ^A2 may have include a halogen atom, -R ^a , -OH, -OR ^a , -SO ₃ H, -SO ₃ ^- G ⁺ , -COOH, -COO ^- T ⁺ , -CO ₂ R ^a , -SR ^a , -SO ₂ R ^a , -SO ₃ R ^a or -SO ₂ NR ^c R ^d . R ^a represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and in the case of -R ^a , R ^a is preferably an alkyl group having 1 to 8 carbon atoms. R ^c and R ^d each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ^c and R ^d may be combined to form a ring containing a nitrogen atom. G ⁺ is Na ⁺ , K ⁺ , or N ⁺ ( ^Re ) ₄ , T ⁺ is Na ⁺ , K ⁺ , or N ⁺ ( ^Rf ) ₄ , the four Re ^'s may be the same or different, and the four Rf ^'s may be the same or different. ^Re and ^Rf each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Examples of the halogen atom as a substituent which the phenylene group represented by A ¹ and A ² may have, and the halogen atom represented by R ¹ to R ⁶ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Preferred substituents which the phenylene groups represented by ^A1 and ^A2 may have are -R ^a , -SO ₃ H, -SO ₃ ^- G ⁺ , -COOH, -COO ^- T ⁺ and -SO ₂ NR ^c R ^d , and in this case, -SO ₃ ^- G ⁺ is preferably -SO ₃ ^- N ⁺ (R ^e ) _4. The most preferred substituent is -R ^a .

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ to R ⁷ , R ^a , R ^e , and R ^f include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; and branched alkyl groups such as isopropyl, isobutyl, isopentyl, and neopentyl groups. However, hydrogen atoms are preferred for R ¹ to R ^7. The alkyl group having 1 to 8 carbon atoms represented by R ^a is more preferably a methyl, ethyl, propyl, or butyl group, and even more preferably a methyl or ethyl group.
The substitution position in the phenylene group may be any position except for the two bonds, and two or more positions may be substituted. When two or more positions are substituted, the substituents may be the same or different.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a , R ^c , and R ^d include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups. The number of carbon atoms in the saturated hydrocarbon group is more preferably 1 to 10, even more preferably 1 to 8, and even more preferably 1 to 5.

Examples of the aralkyl group having 7 to 10 carbon atoms represented by R ^c and R ^d include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Examples of the ring containing a nitrogen atom formed by R ^c and R ^d taken together include the following: In the formula, * represents a bond.

Examples of N ⁺ (R ^e ) ₄ and N ⁺ (R ^f ) ₄ include tetramethylammonium, tetraethylammonium, tetrapropylammonium, and tetrabutylammonium.

Examples of --OR ^a include alkyloxy groups such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

Examples of --CO ₂ R ^a include alkyloxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of --SR ^a include alkylsulfanyl groups such as methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylsulfanyl and icosylsulfanyl groups.

Examples of --SO ₂ R ^a include alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and icosylsulfonyl groups.

Examples of --SO ₃ R ^a include alkyloxysulfonyl groups such as a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

Examples of -SO ₂ NR ^c R ^d include a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfa N-1 substituted sulfamoyl groups such as amoyl group, N-(3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamoyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group, N-(1,5-dimethylhexyl)sulfamoyl group, and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;
Examples of the sulfamoyl group include N,N-disubstituted sulfamoyl groups such as an N,N-dimethylsulfamoyl group, an N,N-ethylmethylsulfamoyl group, an N,N-diethylsulfamoyl group, an N,N-propylmethylsulfamoyl group, an N,N-isopropylmethylsulfamoyl group, an N,N-tert-butylmethylsulfamoyl group, an N,N-butylethylsulfamoyl group, an N,N-bis(1-methylpropyl)sulfamoyl group, and an N,N-heptylmethylsulfamoyl group.

Examples of the hydrocarbon having 1 to 15 carbon atoms which is a divalent group represented by ^L1 and ^L2 include aliphatic hydrocarbons having 1 to 15 carbon atoms, and aromatic hydrocarbons having 6 to 15 carbon atoms, such as benzene and benzene having an alkyl group having 1 to 8 carbon atoms. Examples of the divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms include linear alkanediyl groups having bonds at both ends such as methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl groups, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,2-diyl, butane-2,3-diyl, and 2-methyl Examples of the alkanediyl group include branched alkanediyl groups such as propane-1,1-diyl group, 2-methylpropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, 2-methylbutane-1,4-diyl group, 2-methylbutane-2,3-diyl group, 2-methylbutane-2,4-diyl group, 2-methylbutane-3,3-diyl group, 2-methylbutane-3,4-diyl group, and 2-methylbutane-4,4-diyl group; and cyclic alkanediyl groups such as cyclohexane-1,4-diyl group and cyclohexane-1,4-dimethylene group. Of these, linear alkanediyl groups are preferred.

Examples of benzenes having an alkyl group with 1 to 8 carbon atoms that leads to a divalent aromatic hydrocarbon group with 6 to 15 carbon atoms include methylbenzene, dimethylbenzene, ethylbenzene, propylbenzene, ethyl(methyl)benzene, butylbenzene, and ethyl(dimethyl)benzene. The divalent group formed by removing two hydrogen atoms from the benzene having an alkyl group with 1 to 8 carbon atoms may have two bonds on the alkyl group, two bonds on the benzene ring, or one bond on the alkyl group and one bond on the benzene ring. Of these, the preferred embodiment has one bond on the alkyl group and one bond on the benzene ring.

The divalent hydrocarbon group represented by L ¹ and L ² preferably has 2 to 15 carbon atoms, more preferably 3 to 13 carbon atoms, and even more preferably 4 to 11 carbon atoms.
The --CH ₂ -- contained in the hydrocarbon group may be replaced by --O--, --SO ₂ -- or --NR ⁷ --, but the number of carbon atoms in the hydrocarbon group is defined as the number of carbon atoms before being replaced by these groups.
Among them, the divalent hydrocarbon group represented by ^L1 and ^L2 is particularly preferably a divalent group formed by removing two hydrogen atoms from a benzene having an alkyl group having 1 to 8 carbon atoms, and it is particularly preferable that the alkyl group has one bond and the benzene ring has one bond.
It is preferred that one bond of the alkyl group is bonded to A ¹ or A ² , and one bond of the benzene ring is bonded to CO ₂ H.

As compound (A1), a compound in which *-L ¹ -** (* represents a bond to A ¹ , and ** represents a bond to CO ₂ H) and *-L ² -** (* represents a bond to A ² , and ** represents a bond to CO ₂ H) in formula (A1) are each independently any of the structures represented by formulas (A1a) to (A1h).

*-OR ^31a -** (A1a)
*-OR ^32a -** (A1b)
*-OR ^33a -R ^32a -** (A1c)
*-OR ^32a -R ^33a -** (A1d)
*-SO ₂ -NH-R ^31a -** (A1e)
*-SO ₂ -NH-R ^34a -** (A1f)
*-SO ₂ -NH-R ^33a -R ^34a -** (A1g)
*-SO ₂ -NH-R ^34a -R ^33a -** (A1h)

[In the formula, R ^31a represents an alkanediyl group having 1 to 10 carbon atoms, R ^32a and R ^34a represent phenylene groups to which an alkyl group having 1 to 4 carbon atoms may be bonded, and R ^33a represents an alkanediyl group having 1 to 4 carbon atoms. However, R ^32a has 14 or less carbon atoms, and R ^33a has 13 or less carbon atoms. In addition, the sum of the carbon numbers of R ^32a and R ^33a is 14 or less, and the sum of the carbon numbers of R ^33a and R ^34a is 13 or less. * represents a bond to A ¹ or A ² , and ** represents a bond to CO ₂ H.]

The alkanediyl group having 1 to 10 carbon atoms represented by R ^31a and the alkanediyl group having 1 to 4 carbon atoms represented by R ^33a may be the same as those exemplified as the divalent hydrocarbon groups represented by L ¹ and L ² (preferably those exemplified as the divalent saturated hydrocarbon groups).
The phenylene group which may have an alkyl group having 1 to 4 carbon atoms bonded thereto, represented by R ^32a and R ^34a , includes a benzene having an alkyl group having 1 to 8 carbon atoms, and may be the same as one having two bonds to the benzene. R ^32a and R ^34a are preferably a benzene having an alkyl group having 1 to 4 carbon atoms bonded thereto, and more preferably a 6-methyl-1,3-phenylene group, a 5-methyl-1,3-phenylene group, or a 4-methyl-1,3-phenylene group.

Among (A1a) to (A1h), (A1a) and (A1f) are preferred.

Examples of compound (A1) include compounds represented by formula (A1X). Specific examples of compounds represented by formula (A1X) are represented by numbers (A1X-1) to (A1X-36) in Table 1.

In Table 1, Me represents a methyl group, and RX1 to RX5 and RY1 to RY4 represent groups represented by the following formulas. In the formulas, * represents a bond.

Among these, the compounds represented by numbers (A1X-6) to (A1X-9), the compounds represented by numbers (A1X-15) to (A1X-18), the compounds represented by numbers (A1X-24) to (A1X-27), and the compounds represented by numbers (A1X-33) to (A1X-36) are more preferred.

Compound (A1) can be produced according to known methods.

The content of compound (A1) is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more, relative to the total amount of colorant (A), and is, for example, 70% by mass or less, preferably 60% by mass or less, and may be 50% by mass or less, 40% by mass or less, and more preferably 30% by mass or less.

Compound (A2) is as follows. Compound (A2) also includes its tautomer.

［式（Ａ２）中、Ｒ²¹～Ｒ²⁴は、互いに独立に、水素原子、置換基（ただし、－ＣＯ₂Ｈを除く）を有していてもよい炭素数１～２０の１価の炭化水素基又は－Ｒ⁵⁰－Ｓｉ（Ｒ²⁹）₃を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－ＣＯ－又は－ＮＲ³⁰－で置き換わっていてもよい。ただし、隣接する－ＣＨ₂－が同時に同種の基に置換されることはない。Ｒ²¹及びＲ²²は、一緒になって窒素原子を含む環を形成してもよく、Ｒ²³及びＲ²⁴は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ²⁵は、－ＯＨ、－ＳＯ₃ ^-、－ＳＯ₃Ｈ、－ＳＯ₃ ^-Ｚ⁺、－ＣＯ₂ ^-、－ＣＯ₂Ｈ、－ＣＯ₂ ^-Ｚ⁺、－ＣＯ₂Ｒ²⁸、－ＳＯ₃Ｒ²⁸又は－Ｒ⁵⁰－Ｓｉ（Ｒ²⁹）₃を表す。
Ｒ²⁶及びＲ²⁷は、互いに独立に、水素原子又は炭素数１～６のアルキル基を表す。
ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ²⁵は同一でも異なってもよい。
ａは、０又は１を表す。
Ｘ^-は、任意のアニオンを表す。
Ｚ⁺は、任意のカチオンを表す。
Ｒ²⁸は、炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。Ｒ²⁸が複数存在する場合、複数のＲ²⁸は、それぞれ同一であっても異なっていてもよい。
Ｒ⁵⁰は、炭素数１～１０のアルカンジイル基を表し、該アルカンジイル基を構成する－ＣＨ₂－は、－Ｏ－、－ＣＯ－、－ＮＲ³⁰－、－ＯＣＯ－、－ＣＯＯ－、－ＯＣＯＮＨ－、－ＣＯＮＨ－又は－ＮＨＣＯ－で置き換わっていてもよい。ただし、隣接する－ＣＨ₂－が同時に同種の基に置換されることはない。
Ｒ²⁹は、水素原子、ヒドロキシ基、炭素数１～４のアルキル基又は炭素数１～４のアルコキシ基を表し、複数のＲ²⁹は、それぞれ同一であっても異なっていてもよい。
Ｒ³⁰は、水素原子又は炭素数１～２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。］

[In formula (A2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (excluding -CO ₂ H), or -R ⁵⁰ -Si(R ²⁹ ) ₃ , and -CH ₂ - contained in the hydrocarbon group may be replaced by -O-, -CO- or -NR ³⁰ -, provided that adjacent -CH ₂ - are not simultaneously substituted by the same type of group. R ²¹ and R ²² may be joined together to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be joined together to form a ring containing a nitrogen atom.]
R ²⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ ^- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ²⁸ , -SO ₃ R ²⁸ or -R ⁵⁰ -Si(R ²⁹ ) ₃ .
R ²⁶ and R ²⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, multiple R ²⁵ may be the same or different.
a represents 0 or 1.
X ⁻ represents any anion.
Z ⁺ represents any cation.
R ²⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. When a plurality of R ^28s are present, the plurality of R ^28s may be the same or different.
R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and --CH ₂ -- constituting the alkanediyl group may be replaced by --O--, --CO--, --NR ³⁰ --, --OCO--, --COO--, --OCONH--, --CONH-- or --NHCO--, provided that adjacent --CH ₂ --s are not simultaneously replaced by the same type of group.
R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and multiple R ^29s may be the same or different.
R ³⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Examples of the monovalent hydrocarbon group having 1 to ²⁰ carbon atoms represented by R ^to R include a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, a monovalent unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups.
Examples of the monovalent unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms include linear alkenyl groups such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a hexadecenyl group, an octadecenyl group, and an icosenyl group; and cycloalkenyl groups such as a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.
Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, and a naphthyl group.

Examples of the substituent that the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ²¹ to R ²⁴ may have include a halogen atom, -OH, -OR ^b , -SO ₃ H, -SO ₃ ^- Y ⁺ , -CO ₂ R ^b , -SR ^b , -SO ₂ R ^b , and -SO ₃ R ^b . The R ^b represents a saturated hydrocarbon group having 1 to 20 carbon atoms. Y ⁺ is Na ⁺ , K ⁺ , or N ⁺ (R ^g ) ₄ , and the four R ^{g s} may be the same or different. R ^g represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^b include the groups explained above as the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a .
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^g include the groups explained above as the alkyl group having 1 to 8 carbon atoms represented by R ^e and R ^f .

Examples of N ⁺ (R ^g ) ₄ include tetramethylammonium, tetraethylammonium, tetrapropylammonium, and tetrabutylammonium.

Examples of --OR ^b include alkyloxy groups such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

Examples of --CO ₂ R ^b include alkyloxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of --SR ^b include alkylsulfanyl groups such as a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

Examples of --SO ₂ R ^b include alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and icosylsulfonyl groups.

Examples of --SO ₃ R ^b include alkyloxysulfonyl groups such as a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

Examples of the ring containing a nitrogen atom formed by R ²¹ and R ²² taken together and the ring containing a nitrogen atom formed by R ²³ and R ²⁴ taken together include the following: In the formula, * represents a bond.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ²⁹ include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ²⁹ include a methoxy group, an ethoxy group, a propoxy group, and a tert-butoxy group.

R ²⁹ is preferably a hydroxy group or an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group.

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ⁵⁰ include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a 1-methylethane-1,2-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylbutane-1,4-diyl group, a 2-methylpentane-1,5-diyl group, a 2-methylheptane-1,7-diyl group, and a 2-ethylhexane-1,6-diyl group. Among these, an alkanediyl group having 1 to 6 carbon atoms is preferred, and an alkanediyl group having 1 to 4 carbon atoms is more preferred.

The above-mentioned --R ⁵⁰ --Si(R ²⁹ ) ₃ is preferably a group represented by the following formula (i).

In formula (i), n represents an integer of 1 to 8, R ⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond to the nitrogen atom.

In formula (i), examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁹ include a methyl group, an ethyl group, a propyl group, and a butyl group.

R ⁹ is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

Examples of the group represented by formula (i) include groups represented by the following formulas (i-1) to (i-12). As the group represented by formula (i), groups represented by formula (i-2), groups represented by formula (i-3), groups represented by formula (i-5), and groups represented by formula (i-6) are preferred.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ²⁸ and R ³⁰ include the groups explained above as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ²¹ to R ²⁴ .
The hydrogen atoms contained in the monovalent saturated hydrocarbon group having 1 to ²⁰ carbon atoms represented by ^R and R may be substituted with halogen atoms, and examples of the halogen atoms include chlorine atoms and bromine atoms.

Examples of the cation represented by Z ⁺ include N ⁺ ( ^Ri ) ₄ , Na ⁺ , and K ⁺ , and preferably Na ⁺ or N ⁺ ( ^Ri ) ₄ . The four Ri ^'s may be the same or different. The ^Ri 's represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms and the aralkyl group having 7 to 10 carbon atoms include the groups explained above for R ^c and R ^d .

Examples of N ⁺ (R ⁱ ) ₄ include tetramethylammonium, tetraethylammonium, tetrapropylammonium, and tetrabutylammonium.

Examples of --CO ₂ R ²⁸ include alkyloxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of --SO ₃ R ²⁸ include alkyloxysulfonyl groups such as a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ²⁶ and R ²⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, and a neopentyl group.

Examples of the anion represented by X ⁻ include Cl ⁻ and Br ⁻ .

It is preferable that R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —R ⁵⁰ —Si(R ²⁹ ) ₃ ;
More preferably, at least one of R ²¹ to R ²⁴ is —R ⁵⁰ —Si(R ²⁹ ) ₃ ; or R ²¹ to R ²⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms;
More preferably, at least one of R ²¹ to R ²⁴ is -R ⁵⁰ -Si(R ²⁹ ) ₃ , and the remaining R ²¹ to R ²⁴ are each independently a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms; R ²¹ to R ²⁴ are each independently a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms; or R ²¹ and R ²³ are each independently a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ²² and R ²⁴ are each independently a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms;
Particularly preferred is an embodiment in which at least one of R ²¹ to R ²⁴ is a group represented by formula (i), and the remaining R ²¹ to R ²⁴ are each independently one selected from a methyl group, an ethyl group, a propyl group, a 2-methylphenyl group, and a 2,6-dimethylphenyl group; an embodiment in which R ²¹ to R ²⁴ are each independently one selected from a methyl group, an ethyl group, a propyl group, and a butyl group; or an embodiment in which R ²¹ and R ²³ are each independently a methyl group, an ethyl group, or a propyl group, and R ²² and R ²⁴ are each independently a 2-methylphenyl group or a 2,6-dimethylphenyl group.

R ²⁵ is preferably --OH, --SO ₃ ^-- , --SO ₃ H, --SO ₃ ^{--Z +} , --CO ₂ R ²⁸ , --SO ₃ R ²⁸ or --R ⁵⁰ --Si(R ²⁹ ) ₃ , and more preferably --SO ₃ ^-- , --SO ₃ ^{--Z +} or --SO ₃ H.

R ²⁶ and R ²⁷ are preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.

R ²⁸ is preferably a linear alkyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

R ³⁰ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or a 2-ethylhexyl group.

R ^g is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group.

R ^b is preferably a methyl group, an ethyl group, a propyl group or a butyl group.

R ⁱ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group.

m is preferably 1 to 4, more preferably 1 or 2.

a is preferably 0.

Specific examples of compound (A2) include compounds represented by the following formula:

Examples of the compound (A2) include
Compounds represented by formulas (I-1) to (I-4), compounds represented by formulas (I-25) to (I-28), compounds represented by formulas (I-37) to (I-40), compounds represented by formulas (I-49) to (I-54), compounds represented by formulas (I-55) to (I-62), compounds represented by formulas (I-87) to (I-94), compounds represented by formulas (I-117) to (I-123), compounds represented by formulas (I-124) to (I-133), and compounds represented by formulas (I-137) to (I-160) are preferred, and compounds represented by formulas (I-1) to (I-4), compounds represented by formulas (I-25) to (I-28), compounds represented by formulas (I-55) to (I-62), compounds represented by formulas (I-87) to (I-94), and compounds represented by formulas (I -117), compounds represented by formula (I-119) to formula (I-123), compounds represented by formula (I-124) to formula (I-133), compounds represented by formula (I-137) to formula (I-145), and compounds represented by formula (I-149) to formula (I-157) are more preferred, and compounds represented by formula (I-1) to formula (I-4), compounds represented by formula (I-25) to formula (I-28), compounds represented by formula (I-55) to formula (I-62), compounds represented by formula (I-87) to formula (I-94), compounds represented by formula (I-117), compounds represented by formula (I-119) to formula (I-123), compounds represented by formula (I-124) to formula (I-133), and compounds represented by formula (I-137) to formula (I-145) are even more preferred.

Compound (A2) can be produced according to a known method. Alternatively, commercially available compounds (e.g., "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemical Industry Co., Ltd., "Rhodamin 6G" and "Rhodamin B" manufactured by Taoka Chemical Co., Ltd., and "Acid Red 52" manufactured by Tokyo Chemical Industry Co., Ltd.) may be used.

The content of compound (A2) is, for example, preferably 30% by mass or more, more preferably 40% by mass or more, and may be 50% by mass or more, or may be 60% by mass or more, based on the total amount of colorant (A). The content of compound (A2) is, for example, 99% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less, and even more preferably 85% by mass or less, based on the total amount of colorant (A).

The mass ratio of compound (A1) to compound (A2) (content of compound (A1):content of compound (A2)) is preferably 1:99 to 70:30, more preferably 3:97 to 60:40, and even more preferably 15:85 to 60:40.

The colorant (A) may contain a colorant other than the compound (A1) and the compound (A2) (hereinafter, may be referred to as a “third colorant”).
The third colorant may be either a dye (A3) or a pigment (A4). As the dye (A3), a known dye may be used as long as it does not contain the compound (A1) or the compound (A2), and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include compounds classified as having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Shikisensha). In addition, according to the chemical structure, examples of the dye include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes (excluding the compound (A2)), phthalocyanine dyes, anthraquinone dyes (excluding the compound (A1)), naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

The compounds (A1) and (A2) are classified as dyes, and the total amount of the compounds (A1) and (A2) relative to the total amount of the dyes is, for example, 30% by mass or more, preferably 60% by mass or more, more preferably 90% by mass or more, and may be 95% by mass or more, or may be 100% by mass.

The pigment (A4) is not particularly limited and any known pigment can be used, and examples thereof include pigments classified as pigments in the Color Index (published by the Society of Dyers and Colourists).
Examples of pigments 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, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 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;
blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60;
Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;
green pigments such as C.I. Pigment Green 7, 36, 58;
Brown pigments such as C.I. Pigment Brown 23 and 25;
Examples of the black pigment include black pigments such as C.I. Pigment Black 1 and 7.

The total amount of compound (A1) and compound (A2) is, for example, 30% by mass or more, preferably 60% by mass or more, and more preferably 90% by mass or more, based on the total amount of colorant (A), and may be 95% by mass or more, or may be 100% by mass.

The content of the colorant (A) in the colored curable resin composition is preferably 5 to 60 mass %, more preferably 8 to 55 mass %, and even more preferably 10 to 50 mass %, based on the total amount of solids. When the content of the colorant (A) is within the above range, the color density when made into a color filter is sufficient, and the composition can contain the necessary amounts of resin and polymerizable compound, so that a pattern with sufficient mechanical strength can be formed.
Here, the "total amount of solids" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
Resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably a resin having a structural unit derived from at least one monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. Resin (B) preferably further has at least one structural unit selected from the group consisting of a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, a structural unit derived from a monomer (c) (however different from (a) and (b)) (hereinafter sometimes referred to as "(c)") copolymerizable with (a), and a structural unit having an ethylenically unsaturated bond in a side chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and mono[2-(meth)acryloyloxyethyl]succinate, with acrylic acid, methacrylic acid, and maleic anhydride being preferred.

(b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth)acryloyloxy group.
In this specification, the term "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" have the same meaning.
Examples of (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane, and tetrahydrofurfuryl (meth)acrylate, and preferred are glycidyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, and 3-ethyl-3-(meth)acryloyloxymethyloxetane.

Examples of (c) include methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, and vinyltoluene, and preferably styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide.

A resin having a structural unit with an ethylenically unsaturated bond in the side chain can be produced by adding (b) to a copolymer of (a) and (c), or by adding (a) to a copolymer of (b) and (c). The resin may be a resin obtained by adding (a) to a copolymer of (b) and (c) and then reacting with a carboxylic acid anhydride.

The weight average molecular weight of resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000.
The polydispersity of the resin (B) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.

The acid value of resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 30 to 150 mg-KOH/g, and even more preferably 40 to 135 mg-KOH/g, calculated as solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

The content of resin (B) is preferably 7 to 70 mass %, more preferably 13 to 65 mass %, and even more preferably 17 to 60 mass %, based on the total amount of solids in the colored curable resin composition.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylic acid ester compounds.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

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

When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 7 to 65 mass % relative to the total amount of solids, more preferably 13 to 60 mass %, and even more preferably 17 to 55 mass %.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine. amine, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and the like.

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, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the color filter.

<Polymerization Initiator Auxiliary Agent (D1)>
The colored curable resin composition of the present invention may contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator, or a sensitizer.
Examples of the polymerization initiator aid (D1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, and N-phenylglycine.

When these polymerization initiation aids (D1) are used, the content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with even higher sensitivity, and the productivity of the color filter tends to improve.

<Solvent (E)>
The colored curable resin composition of the present invention preferably contains a solvent (E). The solvent (E) is not particularly limited, and a solvent normally used in the field can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. can be mentioned.

As the solvent (E),
Ester solvents (solvents containing -COO- but not -O- in the molecule) such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone;
Ether solvents (solvents containing -O- but not -COO- in the molecule), such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether;
Ether ester solvents (solvents containing -COO- and -O- in the molecule), such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate;
Ketone solvents (solvents containing —CO— but not —COO— in the molecule), such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, and cyclohexanone;
Alcohol solvents (solvents containing OH in the molecule but not containing —O—, —CO— or —COO—) such as butanol, cyclohexanol, and propylene glycol;
Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and the like.
More preferred solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, ethyl 3-ethoxypropionate, and N-methylpyrrolidone.

When the solvent (E) is contained, the content of the solvent (E) is preferably 60 to 95% by mass, more preferably 65 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of solids in the colored curable resin composition is preferably 5 to 40% by mass, more preferably 8 to 35% by mass. When the content of the solvent (E) is within the above range, the flatness during application is good, and the color density is not insufficient when a color filter is formed, so that the display characteristics tend to be good.

<Leveling Agent (F)>
The colored curable resin composition of the present invention may contain a leveling agent (F). Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
Examples of silicone surfactants include surfactants having siloxane bonds in the molecule.Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), EF-TOP (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemicals Research Institute, Ltd.).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2 mass % relative to the total amount of the colored curable resin composition, and more preferably 0.002 to 0.1 mass %. This content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Fixing agent (G)>
The colored curable resin composition of the present invention may contain a fixing agent (G). As the fixing agent (G), it is preferable to use a silane coupling agent and an alkoxysilane compound. Examples of the silane coupling agent include vinyl group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(2-methoxyethoxy)silane; amino group-containing silane coupling agents such as N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane; epoxy group-containing silane coupling agents such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and 3-methacryloyloxypropyltriethoxysilane; Examples of the silane coupling agents include (meth)acryloyl group-containing silane coupling agents such as acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltriethoxysilane; mercapto group-containing silane coupling agents such as 3-mercaptopropyltrimethoxysilane; isocyanato group-containing silane coupling agents such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane; and alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, and 1,6-bis(trimethoxysilyl)hexane.
Among these, silane coupling agents having a polymerizable ethylenically unsaturated bond-containing group are preferred, vinyl group-containing silane coupling agents and (meth)acryloyl group-containing silane coupling agents are more preferred, and (meth)acryloyl group-containing silane coupling agents are particularly preferred.

The fixing agent (G) is preferably contained when a compound in which at least one of R ²¹ to R ²⁴ is —R ⁵⁰ —Si(R ²⁹ ) ₃ is used as the compound (A2).

When the fixing agent (G) is included, the content of the fixing agent (G) is preferably 0.01 to 10 mass % relative to the total amount of the colored curable resin composition, and more preferably 0.05 to 5 mass %.

<Other ingredients>
The colored curable resin composition of the present invention may contain additives known in the technical field, such as a filler, another polymer compound, an antioxidant, a light stabilizer, and a chain transfer agent, as necessary.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention can be prepared by mixing the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and, if necessary, the polymerization initiator aid (D1), the solvent (E), the leveling agent (F), the fixing agent (G), and other components.

<Color Filter Manufacturing Method>
Methods for producing a colored pattern from the colored curable resin composition of the present invention include photolithography, inkjet printing, printing, etc. Among these, photolithography is preferred.

The colored curable resin composition contains compound (A1) and compound (A2), so that a color filter with excellent light resistance can be produced. The color filter is useful as a color filter for use in display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

The present invention will now be described in more detail with reference to the following examples. In the examples, percentages and parts indicating the content or amount used are by weight unless otherwise specified.

In the following synthesis examples, the structures of the compounds were identified by mass spectrometry (LC: Agilent 1200 model, MASS: Agilent LC/MSD model).

Synthesis Example 1

66.9 parts of chlorosulfuric acid was added to a flask equipped with a cooling tube and a stirrer, and cooled to 10°C or less. 3.6 parts of C.I. Solvent Blue 104 (compound (X-1)) was slowly added while stirring. The reaction solution was then allowed to warm to room temperature and stirred at the same temperature for 6 hours. The resulting reaction solution was added dropwise to 108 parts of ice water to form a suspension, and the precipitated crystals were filtered off, washed thoroughly with ion-exchanged water, and dried overnight at 60°C under reduced pressure to obtain 4.9 parts of a crude product of the compound represented by formula (A-1-IM1). This was purified by silica gel column chromatography (solvent: chloroform) to obtain 3.4 parts of the compound represented by formula (A-1-IM1).

In a flask equipped with a cooling tube and a stirrer, 4.6 parts of methyl 3-amino-4-methylbenzoate and 16.5 parts of chloroform were added and cooled to below 10°C, and a solution of 2.4 parts of the compound represented by formula (A-1-IM1) dissolved in 16.5 parts of chloroform and 2.2 parts of pyridine were successively added dropwise while stirring. The reaction solution was then allowed to warm to room temperature and stirred at the same temperature for 5.5 hours. 150 parts of chloroform and 50 parts of 2N hydrochloric acid were added to the resulting reaction solution to separate the liquids, and the organic layer was washed twice with 50 parts of 2N hydrochloric acid. The resulting organic layer was dried with excess sodium sulfate, and the solution obtained after filtration was evaporated to obtain 3.4 parts of the crude compound represented by formula (A-1-IM2). This was purified by silica gel column chromatography (solvent: chloroform) to obtain 2.8 parts of the compound represented by formula (A-1-IM2).

Identification of the compound represented by formula (A-1-IM2) (mass spectrometry) Ionization mode=ESI ⁺ : m/z=[M+H] ⁺ 929.2
Exact Mass: 928.3

2.5 parts of the compound represented by formula (A-1-IM2), 35 parts of N-methylpyrrolidone, and 17 parts of 8% aqueous sodium hydroxide solution were added to a flask equipped with a cooling tube and a stirrer, and the mixture was stirred at 50°C for 5 hours. The resulting reaction liquid was added to 175 parts of 2N hydrochloric acid to form a suspension, and the precipitated crystals were filtered off, washed thoroughly with ion-exchanged water, and dried overnight at 60°C under reduced pressure to obtain 2.1 parts of the compound represented by formula (A1X-36) (hereinafter sometimes referred to as "dye (A1X-36)").

Identification of the compound represented by formula (A1X-36) (mass spectrometry) Ionization mode=ESI ⁺ : m/z=[M+H] ⁺ 901.2
Exact Mass: 900.3

[Synthesis Example 2]

40.6 parts of the compound represented by formula (VI-1) and 8 parts of diethylamine (Tokyo Chemical Industry Co., Ltd.) were mixed in the presence of 50 parts of N-methylpyrrolidone under light-shielded conditions, and stirred at 30° C. for 3 hours. The resulting reaction solution was cooled to room temperature, and then added to a mixed solution of 400 parts of water and 20 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, whereby crystals were precipitated. The precipitated crystals were collected as a residue by suction filtration and then dried to obtain 44 parts of the compound represented by formula (I-1-A).
Next, 44 parts of the compound represented by formula (I-1-A) and 21.4 parts of trimethoxy[3-(methylamino)propyl]silane (manufactured by Tokyo Chemical Industry Co., Ltd.) were heated at 100° C. for 5 hours in the presence of 50 parts of N-methylpyrrolidone. The resulting reaction liquid was cooled to room temperature and then filtered, and the resulting residue was washed with 100 parts of water. The resulting crystals were dried to obtain 52 parts of the compound represented by formula (I-1) (hereinafter sometimes referred to as "dye (I-1)").

Identification of the compound represented by formula (I-1) (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 599.2
Exact Mass: 598.1

[Synthesis Example 3]
A compound represented by formula (I-132) (hereinafter, sometimes referred to as “dye (I-132)”) was synthesized by the method described in JP2013-64096A.

Identification of the compound represented by formula (I-132) (mass spectrometry) Ionization mode=ESI+: m/z=[M+H] ^+659.9
Exact Mass: 658.9

Synthesis Example 4
A compound represented by formula (I-144) (hereinafter sometimes referred to as “dye (I-144)”) was synthesized by the method described in WO 2014/192973.

(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 442.1
Exact Mass: 441.1

Synthesis Example 5
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85°C while stirring. Next, a mixed solution of 38 parts of acrylic acid, 25 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl acrylate (content ratio is 1:1 in molar ratio), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 5 parts of 2,2-azobisisobutyronitrile dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a viscosity of 23 mPas measured with a Brookfield viscometer (23°C) and a solid content of 25.6%. The weight average molecular weight Mw of the produced copolymer was 8.0 x 10 ³ , the degree of dispersion was 2.1, and the acid value calculated as solid content was 109 mg-KOH/g. Resin B-1 has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40°C
Solvent: THF (tetrahydrofuran)
Test solution concentration: 25 mg/mL (solvent: THF)
Flow rate: 1.0mL/min
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight calculated in terms of polystyrene obtained above was taken as the polydispersity (Mw/Mn).

Example 1
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Dye (I-1) 24 parts (G) Fixing agent: 3-methacryloxypropyltrimethoxysilane 23 parts (E) Solvent: Propylene glycol monomethyl ether acetate 41 parts (E) Solvent: Diacetone alcohol 371 parts are mixed, and then
(A) Colorant: Dye (A1X-36) 5 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (TORAY SILICONE SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 396 parts (E) Solvent: N-methylpyrrolidone 95 parts were mixed to obtain a colored curable resin composition.

Example 3
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Dye (I-1) 9 parts (G) Fixing agent: 3-methacryloxypropyltrimethoxysilane 9 parts (E) Solvent: Propylene glycol monomethyl ether acetate 16 parts (E) Solvent: Diacetone alcohol 143 parts are mixed, and then
(A) Colorant: Dye (A1X-36) 11 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (TORAY SILICONE SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 401 parts (E) Solvent: N-methylpyrrolidone 214 parts were mixed to obtain a colored curable resin composition.

Example 4
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Dye (I-1) 20 parts (G) Fixing agent: 3-methacryloxypropyltrimethoxysilane 20 parts (E) Solvent: Propylene glycol monomethyl ether acetate 35 parts (E) Solvent: Diacetone alcohol 316 parts are mixed, and then
(A) Colorant: Dye (A1X-36) 2 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (TORAY SILICONE SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 456 parts (E) Solvent: N-methylpyrrolidone 43 parts were mixed to obtain a colored curable resin composition.

Comparative Example 1
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Dye (I-1) 23 parts (G) Fixing agent: 3-methacryloxypropyltrimethoxysilane 22 parts (E) Solvent: Propylene glycol monomethyl ether acetate 39 parts (E) Solvent: Diacetone alcohol 355 parts are mixed, and then
(B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 509 parts were mixed to obtain a colored curable resin composition.

<Preparation of Colored Pattern>
A colored curable resin composition was applied by spin coating onto a 5 cm square glass substrate (Eagle 2000; Corning Incorporated), and then prebaked at 100 ° C. for 3 minutes to obtain a colored composition layer. After cooling, the substrate on which the colored composition layer was formed and a quartz glass photomask were spaced 100 μm apart, and the substrate was irradiated with light at an exposure dose of 150 mJ / cm ² (based on 365 nm) under atmospheric conditions using an exposure machine (TME-150RSK; Topcon Corporation). As the photomask, one on which a 100 μm line and space pattern was formed was used. The colored composition layer after light irradiation was immersed and developed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide for 60 seconds at 24 ° C., washed with water, and then post-baked in an oven at 230 ° C. for 20 minutes to obtain a colored pattern.

<Film thickness measurement>
The film thickness of the resulting colored pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Shinku Gijutsu Co., Ltd.).

<Light resistance evaluation>
An ultraviolet ray cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co.; cuts light of 380 nm or less) was placed on the obtained colored pattern, and the pattern was irradiated with light from a xenon lamp for 48 hours using a light resistance tester (Suntest CPS+; manufactured by Toyo Seiki Co., Ltd.).
Before and after irradiation, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) and stimulus value Y in the CIE XYZ color system were measured using the characteristic function of C light source. From the measured values, the color difference ΔEab* was calculated according to the method described in JIS Z 8730:2009 (7. Method of calculating color difference), and the results are shown in Table 2. The smaller ΔEab* means the smaller the color change. The differences in x, y, and Y before and after the test are also shown in Table 2 as Δx, Δy, and ΔY, respectively.

Example 5
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Dye (I-132) 20 parts (A) Colorant: Dye (A1X-36) 5 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 591 parts (E) Solvent: N-methylpyrrolidone 95 parts of (E) Solvent: diacetone alcohol 61 parts were mixed to obtain a colored curable resin composition.

Comparative Example 2
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Dye (I-132) 19 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 655 parts (E) Solvent: Diacetone alcohol 59 parts were mixed to obtain a colored curable resin composition.

In the same manner as in Example 1, colored patterns were prepared from the colored curable resin compositions of Example 5 and Comparative Example 2, and the film thickness and light resistance of the obtained colored patterns were measured. The results are shown in Table 3.

Example 6
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Acid Red 52 (Tokyo Chemical Industry Co., Ltd.) 20 parts (A) Colorant: Dye (A1X-36) 5 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 276 parts (E) Solvent: 95 parts of N-methylpyrrolidone and (E) Solvent: 376 parts of diacetone alcohol were mixed to obtain a colored curable resin composition.
Incidentally, Acid Red 52 is a compound represented by formula (I-150).

Comparative Example 3
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Acid Red 52 (Tokyo Chemical Industry Co., Ltd.) 19 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 355 parts (E) Solvent: Diacetone alcohol 359 parts of the components were mixed to obtain a colored curable resin composition.

In the same manner as in Example 1, colored patterns were prepared from the colored curable resin compositions of Example 6 and Comparative Example 3, and the film thickness and light resistance of the obtained colored patterns were measured. The results are shown in Table 4.

Example 7
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Dye (I-144) 20 parts (A) Colorant: Dye (A1X-36) 5 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 276 parts (E) Solvent: N-methylpyrrolidone 95 parts of (E) Solvent: diacetone alcohol 376 parts were mixed to obtain a colored curable resin composition.

Comparative Example 4
<Preparation of Colored Curable Resin Composition>
(A) Colorant: Dye (I-144) 19 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation) 7 parts (F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.) 0.1 parts (E) Solvent: Propylene glycol monomethyl ether acetate 355 parts (E) Solvent: Diacetone alcohol 359 parts were mixed to obtain a colored curable resin composition.

In the same manner as in Example 1, colored patterns were prepared from the colored curable resin compositions of Example 7 and Comparative Example 4, and the film thickness and light resistance of the obtained colored patterns were measured. The results are shown in Table 5.

It was confirmed that the color filter obtained using the colored curable resin composition of the examples exhibited superior light resistance.

Claims (3)

Contains a colorant, an alkali-soluble resin, a polymerizable compound, and a polymerization initiator,
A colored curable resin composition, comprising a colorant comprising a compound represented by formula (A1) and a compound represented by formula (A2).

[In formula (A1),
A ¹ and A ² each independently represent a phenylene group which may have a substituent.
^L1 and ^L2 each independently represent a divalent hydrocarbon group having 1 to 15 carbon atoms, and _-CH2- contained in the hydrocarbon group may be replaced by -O-, _-SO2- or ^-NR7- , provided that adjacent _-CH2- are not simultaneously replaced by the same type of group.
R ¹ to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[In formula (A2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (excluding -CO ₂ H), or -R ⁵⁰ -Si(R ²⁹ ) ₃ , and -CH ₂ - contained in the hydrocarbon group may be replaced by -O-, -CO- or -NR ³⁰ -, provided that adjacent -CH ₂ - are not simultaneously substituted by the same type of group. R ²¹ and R ²² may be joined together to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be joined together to form a ring containing a nitrogen atom.]
R ²⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ ^- , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ²⁸ , -SO ₃ R ²⁸ or -R ⁵⁰ -Si(R ²⁹ ) ₃ .
R ²⁶ and R ²⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, multiple R ²⁵ may be the same or different.
a represents 0 or 1.
X ⁻ represents any anion.
Z ⁺ represents any cation.
R ²⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. When a plurality of R ^28s are present, the plurality of R ^28s may be the same or different.
R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and --CH ₂ -- constituting the alkanediyl group may be replaced by --O--, --CO--, --NR ³⁰ --, --OCO--, --COO--, --OCONH--, --CONH-- or --NHCO--, provided that adjacent --CH ₂ --s are not simultaneously replaced by the same type of group.
R ²⁹ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and multiple R ^29s may be the same or different.
R ³⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. A color filter formed from the colored curable resin composition according to claim 1. A display device including the color filter according to claim 2.