JP7548834B2 - Colored resin composition - Google Patents

Description

The present invention relates to a colored resin composition. More specifically, the present invention relates to a colored resin composition containing a phthalocyanine compound.

Color filters used in liquid crystal display devices and the like are manufactured from colored curable resin compositions. Phthalocyanine dyes are known as colorants contained in colored curable resin compositions for forming color filters (Patent Document 1).

International Publication No. 2016/076028

In recent years, there has been a demand for improved brightness of the green color of color filters. The object of the present invention is to provide a color filter having high brightness of green, and a colored resin composition useful for producing the color filter.

The present invention includes the following inventions.
[1] A composition comprising a colorant and a resin,
A colored resin composition, characterized in that the colorant comprises a phthalocyanine compound in which one or more hydrogen atoms are substituted with _SF5 .
[2] The colored resin composition according to [1], wherein the colorant contains a compound represented by the following formula (1a) and/or (1b):

［式（１ａ）、式（１ｂ）中、
Ｒ^xは、それぞれ独立にＳＦ₅、又は１つ以上の水素原子がＳＦ₅に置換された炭素数１～２０の炭化水素基を表し、
ｍは、１～１６の整数を表し、
Ｒ^yは、それぞれ独立に置換基を有していてもよい炭素数１～２０の炭化水素基を表し、
ｎは、０～１５の整数を表し、
Ｍは、置換基を有していてもよい金属元素、又は置換基を有していてもよい半金属元素を表し、
Ｒ^x及びＲ^yで表される炭化水素基の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ₂－、－ＮＨ－、－ＣＯ－、又は－ＣＯ₂－に置き換わっていてもよい。］
［３］前記式（１ａ）で表される化合物が下記式（２ａ）で表される化合物であり、前記式（１ｂ）で表される化合物が下記式（２ｂ）で表される化合物である［２］に記載の着色樹脂組成物。

[In formula (1a) and formula (1b),
R ^x 's each independently represent SF ₅ or a hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with SF ₅ ;
m represents an integer from 1 to 16;
R ^y each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent;
n represents an integer from 0 to 15;
M represents a metal element which may have a substituent, or a metalloid element which may have a substituent,
The --CH ₂ -- of the hydrocarbon group represented by R ^x and R ^y may be replaced by --O--, --S--, --SO ₂ --, --NH--, --CO--, or --CO ₂ --. good.]
[3] The compound represented by formula (1a) is a compound represented by the following formula (2a), and the compound represented by formula (1b) is a compound represented by the following formula (2b): The colored resin composition according to [2].

［式（２ａ）、式（２ｂ）中、Ｒ^x、Ｒ^y、Ｍは、それぞれ前記と同じ意味を表し、
ｏは、１～４の整数を表し、
ｐは、０～３の整数を表す。］
［４］前記着色剤が、黄色顔料及び緑色顔料よりなる群から選ばれる少なくとも１種の顔料を含む［１］～［３］のいずれかに記載の着色樹脂組成物。
［５］［１］～［４］のいずれかに記載の着色樹脂組成物と、重合性化合物と、重合開始剤とを含む着色硬化性樹脂組成物。
［６］［５］に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。
［７］［６］に記載のカラーフィルタを含む表示装置。

[In formula (2a) and formula (2b), R ^x , R ^y and M each have the same meaning as defined above,
o represents an integer of 1 to 4;
p represents an integer of 0 to 3.
[4] The colored resin composition according to any one of [1] to [3], wherein the colorant comprises at least one pigment selected from the group consisting of yellow pigments and green pigments.
[5] A colored curable resin composition comprising the colored resin composition according to any one of [1] to [4], a polymerizable compound, and a polymerization initiator.
[6] A color filter formed from the colored curable resin composition according to [5].
[7] A display device comprising the color filter according to [6].

The present invention provides a color filter having a high green brightness and a colored resin composition useful for producing the color filter.

The colored resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as colorant (A)) and a resin (hereinafter, sometimes referred to as resin (B)). The colorant contains a phthalocyanine compound in which one or more hydrogen atoms are substituted with _SF5 . This can improve the brightness of green. Each component of the colored resin composition will be described below. In this specification, the compounds exemplified as each component can be used alone or in combination, unless otherwise specified.

<Colorant (A)>
The colorant (A) preferably contains a compound represented by the following formula (1a) (hereinafter may be referred to as compound (1a)) and/or a compound represented by the following formula (1b) (hereinafter may be referred to as compound (1b)), and more preferably contains compound (1a). The colorant (A) may contain compound (1a) and compound (1b), or may contain compound (1a) or compound (1b).

<Compound (1a), compound (1b)>
Compound (1a) is a compound represented by the following formula (1a), and compound (1b) is a compound represented by the following formula (1b).

［式（１ａ）、式（１ｂ）中、
Ｒ^xは、それぞれ独立にＳＦ₅、又は１つ以上の水素原子がＳＦ₅に置換された炭素数１～２０の炭化水素基を表し、
ｍは、１～１６の整数を表し、
Ｒ^yは、それぞれ独立に置換基を有していてもよい炭素数１～２０の炭化水素基を表し、
ｎは、０～１５の整数を表し、
Ｍは、置換基を有していてもよい金属元素、又は置換基を有していてもよい半金属元素を表し、
Ｒ^x及びＲ^yで表される炭化水素基の－ＣＨ₂－は、－Ｏ－、－Ｓ－、－ＳＯ₂－、－ＮＨ－、－ＣＯ－、又は－ＣＯ₂－に置き換わっていてもよい。］

[In formula (1a) and formula (1b),
R ^x 's each independently represent SF ₅ or a hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with SF ₅ ;
m represents an integer from 1 to 16;
R ^y each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent;
n represents an integer from 0 to 15;
M represents a metal element which may have a substituent, or a metalloid element which may have a substituent,
The --CH ₂ -- of the hydrocarbon group represented by R ^x and R ^y may be replaced by --O--, --S--, --SO ₂ --, --NH--, --CO--, or --CO ₂ --. good.]

R ^y may be a substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms, but is preferably an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The substituent does not include _SF5 .

Examples of R ^y include an aliphatic hydrocarbon group and a group having an aromatic ring (hereinafter sometimes referred to as an aromatic ring-containing group).

The aliphatic hydrocarbon group in ^Ry may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The aliphatic hydrocarbon group may be linear or alicyclic. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. When the aliphatic hydrocarbon group has a substituent, the number of carbon atoms in the substituent is included in the number of carbon atoms.

Examples of the chain saturated hydrocarbon group for ^Ry include linear alkyl groups 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;
branched alkyl groups such as an isopropyl group, a (1-ethyl)propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a (1-ethyl)butyl group, a (2-ethyl)butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a (2-methyl)pentyl group, an isohexyl group, a (5-methyl)hexyl group, and a (3-ethyl)heptyl group;

Examples of the chain unsaturated hydrocarbon group for R ^y include alkenyl groups such as a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a (1-methyl)ethenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butadienyl group, a (1-(2-propenyl))ethenyl group, a (1,2-dimethyl)propenyl group, and a 2-pentenyl group.

Examples of the alicyclic saturated hydrocarbon group for ^Ry include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., norbornyl group, adamantyl group, bicyclo[2.2.2]octyl group, etc. Examples of the alicyclic unsaturated hydrocarbon group include cycloalkenyl groups such as cyclohexenyl group (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group, cyclooctenyl group, etc.

The aliphatic hydrocarbon group for ^Ry may be formed by a combination of linear and alicyclic hydrocarbon groups, and examples thereof include a 1-methylcyclopropyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a 2,4,6-trimethylcyclohexyl group, a 2,2,6,6-tetramethylcyclohexyl group, a 4-pentylcyclohexyl group, a 4-octylcyclohexyl group, a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group, and an adamantylmethyl group.

The -CH ₂ - of the aliphatic hydrocarbon group for R ^y may be replaced by -O-, -S-, -SO ₂ -, -NH-, -CO-, -CO ₂ -, etc. Examples of the aliphatic hydrocarbon group substituted with -CH ₂ - include alkoxy groups such as methoxy group and ethoxy group, alkylthio groups such as methylthio group and ethylthio group, alkylsulfonyl groups such as methylsulfonyl group and ethylsulfonyl group, alkylamino groups such as monomethylamino group, dimethylamino group, monoethylamino group and diethylamino group, alkylcarbonyl groups such as acetyl group and propionyl group, and alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group.

The aliphatic hydrocarbon group in R ^y may have a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, an amino group which may be substituted, a hydroxy group, a carbamoyl group, an acetyl group, a carboxy group, a silyl group, an alkylsilyl group having 3 to 10 carbon atoms, and an alkoxysilyl group having 3 to 10 carbon atoms. An alkylsilyl group having 3 to 10 carbon atoms and an alkoxysilyl group having 3 to 10 carbon atoms are preferred. The alkylsilyl group and the alkoxysilyl group can suppress dye migration. Examples of the alkylsilyl group having 3 to 10 carbon atoms include a trimethylsilyl group and a triethylsilyl group. Examples of the alkoxysilyl group having 3 to 10 carbon atoms include a trimethoxysilyl group and a triethoxysilyl group. Examples of the aliphatic hydrocarbon group having an alkylsilyl group having 3 to 10 carbon atoms as a substituent include a trimethylsilylalkyl group, a triethylsilylalkyl group, a trimethoxysilylalkyl group, and a triethoxysilylalkyl group, in which the alkyl group has 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.

Examples of the aromatic ring-containing group for ^Ry include aromatic hydrocarbon groups, aromatic hydrocarbon groups to which an aliphatic hydrocarbon group is bonded, etc. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, an anthryl group, and a pyrenyl group.

Examples of the aromatic hydrocarbon group having an aliphatic hydrocarbon group bonded thereto include aralkyl groups such as a benzyl group, a phenethyl group, and a 1-methyl-1-phenylethyl group;
Arylalkenyl groups such as a phenylethenyl group (a phenylvinyl group) and the like;
Arylalkynyl groups such as a phenylethynyl group;
Alkylaryl groups such as o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, and 4-butylphenyl group;
Aryl groups to which an alkanediyl group is bonded, such as a 2,3-dihydro-4-indenyl group, a 1,2,3,5,6,7-hexahydro-4-s-indacenyl group, a 5,6,7,8-tetrahydro-1-naphthyl group, or a 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl group;
An aryl group having one or more aryl groups bonded thereto, such as a biphenylyl group or a terphenylyl group;
Examples thereof include a cyclohexylmethylphenyl group, a benzylphenyl group, and a (dimethyl(phenyl)methyl)phenyl group.

The --CH ₂ -- of the aromatic hydrocarbon group to which the aliphatic hydrocarbon group is bonded may be replaced by --O--, --S--, --SO ₂ --, --NH--, --CO--, --CO ₂ --, etc. Examples of the aromatic hydrocarbon group to which an aliphatic hydrocarbon group to which --CH ₂ -- is bonded include aryloxy groups such as a phenyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group;
Arylthio groups such as a phenylthio group, a 1-naphthylthio group, or a 2-naphthylthio group;
arylsulfonyl groups such as a phenylsulfonyl group, 1-naphthylsulfonyl, 2-naphthylsulfonyl, and the like;
Arylamino groups such as a monophenylamino group or a diphenylamino group;
aralkylamino groups such as a benzylamino group;
Arylcarbonyl groups such as a benzoyl group, a 1-naphthylcarbonyl group, or a 2-naphthylcarbonyl group;
An aryloxycarbonyl group such as a phenyloxycarbonyl group, a 1-naphthyloxycarbonyl group, or a 2-naphthyloxycarbonyl group; or the like.

The aromatic ring-containing group may have a substituent bonded to the aromatic ring hydrocarbon group or the aliphatic hydrocarbon group bonded to the aromatic hydrocarbon group, and preferably has a substituent bonded to the aliphatic hydrocarbon group bonded to the aromatic hydrocarbon group. Examples of the substituent include the same ones as those exemplified as the substituents of the aliphatic hydrocarbon group, and alkylsilyl groups having 3 to 10 carbon atoms and alkoxysilyl groups having 3 to 10 carbon atoms are preferred. Examples of aliphatic hydrocarbon groups substituted with alkylsilyl groups having 3 to 10 carbon atoms and alkoxysilyl groups having 3 to 10 carbon atoms include trimethylsilylalkyl groups, triethylsilylalkyl groups, trimethoxysilylalkyl groups, and triethoxysilylalkyl groups, in which the alkyl group has 1 to 4 carbon atoms.

The number of carbon atoms in the aliphatic hydrocarbon group of the aromatic ring-containing group is preferably 1 to 5, and more preferably 1 to 2.

The number of carbon atoms in the aromatic ring-containing group is preferably 6 to 20, more preferably 6 to 15, even more preferably 6 to 10, and particularly preferably 6. If the aromatic ring has a substituent, the number of carbon atoms in the substituent is included in the number of carbon atoms.

In formula (1a) and formula (1b), n is preferably an integer of 0 to 15, more preferably an integer of 0 to 8, still more preferably an integer of 0 to 4, still more preferably an integer of 0 to 2, and particularly preferably 0. When compound (1a) has a plurality of R ^y's , the R ^y's may be the same or different from each other. When compound (1b) has a plurality of R ^y's , the R ^y's may be the same or different from each other.

When compound (1a) has a plurality of R ^x , R ^x may be the same or different from each other. When compound (1b) has a plurality of R ^x , R ^x may be the same or different from each other.

R ^x is preferably SF _5. R ^x may also be a hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with SF ₅ , and the hydrocarbon group can be selected from the same groups as R ^y described above, including aliphatic hydrocarbon groups and groups having an aromatic ring (aromatic ring-containing groups). The number of SF ₅ substituted per one hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1. The hydrocarbon group is preferably a hydrocarbon group having no substituents other than SF ₅ .

^Rx is preferably an aromatic ring-containing group in which one or more hydrogen atoms are substituted with _SF5 , and more preferably an aromatic hydrocarbon group in which one or more hydrogen atoms are substituted with _SF5 . In the aromatic ring-containing group in which one or more hydrogen atoms are substituted with _SF5 , _SF5 is preferably bonded to the meta position and/or para position relative to the bond of the aromatic ring-containing group, and more preferably _SF5 is bonded to the para position. Examples of such aromatic ring-containing groups include groups represented by the formula (Ar- _mSF5 ) and the formula (Ar- _pSF5 ) described below.

m is preferably an integer from 1 to 16, more preferably an integer from 2 to 12, even more preferably an integer from 3 to 9, even more preferably an integer from 4 to 8, and particularly preferably 4. The sum of n and m is preferably an integer from 1 to 16, more preferably an integer from 2 to 12, even more preferably an integer from 3 to 9, even more preferably an integer from 4 to 8, and particularly preferably 4.

M is a metal element which may have a substituent, or a metalloid element which may have a substituent.

Metal elements which may have a substituent include metal elements and metal elements having a substituent. Metal elements include alkali metals, alkaline earth metals, transition metals, lanthanoid metals, and actinoid metal elements. Specific examples of metal elements include lithium, sodium, potassium, magnesium, calcium, scandium, yttrium, titanium, zirconium, chromium, manganese, molybdenum, iron, ruthenium, cobalt, rhodium, nickel, palladium, nickel, copper, zinc, aluminum, gallium, indium, tin, lanthanum, and uranium. Of these, copper, zinc, and aluminum are preferred.

Examples of the substituent include an oxygen atom, a hydroxyl group, a halogen atom, a phosphate group, a sulfonic acid group, a carboxylate group, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

Specific examples of the metal element having a substituent include metal oxides such as lithium oxide, magnesium oxide, calcium oxide, titanium oxide, chromium oxide, manganese oxide, molybdenum oxide, iron oxide, ruthenium oxide, copper oxide, zinc oxide, aluminum oxide, gallium oxide, lanthanum oxide, and uranium oxide;
Metal hydroxides such as aluminum hydroxide, indium hydroxide, and thallium hydroxide;
Metal halides such as copper fluoride, zinc fluoride, aluminum fluoride, copper chloride, zinc chloride, and aluminum chloride;
Metal phosphates such as copper phosphate, zinc phosphate, and aluminum phosphate;
Metal sulfonates such as copper sulfonate, zinc sulfonate, and aluminum sulfonate;
Metal carboxylates such as copper carboxylate, zinc carboxylate, and aluminum carboxylate;
Hydrocarbon-containing metals such as hydrocarbon-containing aluminum represented by --Al(R ^z )--, where R ^z is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms;

Metalloid elements that may have a substituent include metalloid elements and metalloid elements that have a substituent. Metalloid elements are elements that have intermediate properties between metals and nonmetals. Examples of metalloid elements include boron, silicon, arsenic, germanium, and lead. Examples of substituents include the same groups as the substituents of the metal elements listed above.

Examples of the metalloid elements having a substituent include metalloid oxides such as boron oxide, silicon oxide, arsenic oxide, germanium oxide, and lead oxide;
Metalloid hydroxides such as boron hydroxide, silicon hydroxide, and lead hydroxide;
Metalloid halides such as boron fluoride, silicon fluoride, lead fluoride, boron chloride, silicon chloride, and lead chloride;
Metalloid phosphates such as boron phosphate, silicon phosphate, and lead phosphate;
Sulfonated metalloids such as boron sulfonates, silicon sulfonates, and lead sulfonates;
Carboxylated metalloids such as boron carboxylates, silicon carboxylates, and lead carboxylates;
Hydrocarbon-containing semimetals such as hydrocarbon-containing silicon represented by --Si(R ^z1 )(R ^z2 )--, where R ^z1 and R ^z2 are each independently an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms;

It is preferable that compound (1a) is a compound represented by the following formula (2a) (hereinafter, may be referred to as compound (2a)). It is also preferable that compound (1b) is a compound represented by the following formula (2b) (hereinafter, may be referred to as compound (2b)).

［式（２ａ）、式（２ｂ）中、Ｒ^x、Ｒ^y、Ｍは、それぞれ上記と同じ意味を表し、
ｏは、１～４の整数を表し、
ｐは、０～３の整数を表す。］

[In formula (2a) and formula (2b), R ^x , R ^y and M each have the same meaning as defined above,
o represents an integer of 1 to 4;
p represents an integer of 0 to 3.

In formula (2a) and formula (2b), o is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and particularly preferably 1. p is preferably an integer of 0 to 3, more preferably an integer of 0 to 1, and particularly preferably 0. The sum of o and p is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and particularly preferably 1.

Compound (1a) is preferably a compound represented by the following formula (3a). Compound (1b) is preferably a compound represented by the following formula (3b).

[In formula (3a) and formula (3b), at least one of R ^a to R ^d is independently the same group as R ^x above, and the others are a hydrogen atom or the same group as R ^y above. M has the same meaning as above.]

Of R ^a to R ^d , it is preferred that R ^a or R ^d are each independently a group similar to the above R ^x and the others are the same group as the above R ^y or a hydrogen atom, or that R ^b or R ^c are each independently a group similar to the above R ^x and the others are the same group as the above R ^y or a hydrogen atom.
Among R ^a to R ^d , it is more preferable that R ^b or R ^c each independently represents a group similar to R ^x above, and the others each represent a group similar to R ^y above or a hydrogen atom;
It is more preferable that R ^b or R ^c each independently represents the same group as R ^x above, and the others each represent a hydrogen atom.
It is even more preferred that R ^b or R ^c are each independently SF ₅ and the other is a hydrogen atom.

Among R ^a to R ^d , it is more preferable that R ^a or R ^d is each independently a group similar to R ^x above, and the others are a group similar to R ^y above or a hydrogen atom;
It is more preferable that R ^a or R ^d is each independently the same group as R ^x above, and the others are hydrogen atoms,
It is even more preferred that R ^a or R ^d each independently represents an aromatic ring-containing group in which one or more hydrogen atoms have been replaced with SF ₅ , and the remaining are hydrogen atoms.

In the aromatic ring-containing group in which one or more hydrogen atoms are substituted with _SF5 , _SF5 is preferably bonded to the meta-position and/or para-position relative to the bond of the aromatic ring-containing group, and more preferably bonded to the para _- position. Examples of such aromatic ring-containing groups include groups represented by the formula (Ar- _mSF5 ) and the formula (Ar- _pSF5 ) described below.

As compound (1a) and compound (1b), compounds (a1) to (a20) shown in Table 1 below and represented by formula (4a) below, and compounds (b1) to (b20) shown in Table 2 below and represented by formula (4b) below are preferred.

In formula 4a and formula 4b, R ^x and M have the same meaning as above. In Tables 1 and 2, SF ₅ , CSF ₅ , CCSF ₅ , Ar-mSF ₅ and Ar-pSF ₅ respectively represent groups represented by the following formulas (SF ₅ ), (CSF ₅ ), (CCSF ₅ ), (Ar-mSF ₅ ) and (Ar-pSF ₅ ).

As compounds (1a) and (1b), compounds (a1) to (a15) and compounds (b1) to (b15) are more preferred, compounds (a1) to (a15) are even more preferred, compounds (a1), (a4) to (a6), (a9) to (a11), (a14) and (a15) are even more preferred, and compounds (a1), (a6) and (a11) are particularly preferred.

As compounds (1a) and (1b), compounds (b1) to (b15) are more preferred, compounds (b4), (b5), (b9), (b10), (b14), and (b15) are even more preferred, and compounds (b5), (b10), and (b15) are particularly preferred.

The method for producing compound (1a) and compound (1b) is not particularly limited, but they can be produced by referring to the examples described in Japanese Patent No. 6206977.

Compound (1a) and compound (1b) are preferably soluble in an organic solvent having a solubility parameter (SP value) of less than 11.0 (cal/cm ³ ) ^1/2 , such as propylene glycol monomethyl ether acetate. The solubility and poor solubility can be evaluated by the following method.

0.1 g of the compound is added to a 20 mL sample vial, and an organic solvent is added using a 10 mL volumetric pipette. The vial is then closed and ultrasonically treated for 3 minutes. The resulting solution is left to stand in a water bath at 23°C for 60 minutes. 5 mL of the supernatant is filtered through a PTFE 5 μm membrane filter, and then filtered through a 0.25 μm membrane filter to remove insoluble matter. The absorption spectrum of the resulting filtrate is measured using a 1 cm cell with an ultraviolet-visible spectrophotometer (e.g., Shimadzu UV-2500PC), and the absorbance (abs) at the maximum absorption wavelength of the compound is determined. At this time, if the absorbance (abs) is less than 40% of the upper measurement limit (in the case of Shimadzu UV-2500PC, the absorbance (abs) is less than 2), the compound is evaluated as being poorly soluble, and if it is 40% or more of the upper measurement limit, the compound is evaluated as being soluble.

The content of compound (1a) and compound (1b) is preferably 40 to 100 mass%, more preferably 60 to 90 mass%, and even more preferably 70 to 80 mass% of the total amount of colorant (A). When the colored resin composition contains both compound (1a) and compound (1b), the content of compound (1a) and compound (1b) means the total content of these compounds.

The content of compound (1a) in the total amount of colorant (A) is preferably 40 to 100 mass%, more preferably 60 to 90 mass%, and even more preferably 70 to 80 mass%.

The content of compound (1a) and compound (1b) is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 12 to 50 parts by mass, per 100 parts by mass of resin (B) (solid content). When the colored resin composition contains both compound (1a) and compound (1b), the content of compound (1a) and compound (1b) means the total amount of these.

<Colorant (A1)>
The colored resin composition of the present invention may contain, as the colorant (A), a dye other than the compound (1a) and the compound (1b) (hereinafter, sometimes referred to as dye (A1-1)) and/or a pigment (hereinafter, sometimes referred to as pigment (A1-2)) (hereinafter, the dye (A1-1) and the pigment (A1-2) may be collectively referred to as colorant (A1)). These may be used alone or in combination of two or more kinds.

As long as the dye (A1-1) does not include the compounds (1a) and (1b), it is not particularly limited and known dyes can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Irosensha). In addition, examples of dyes that can be used according to their chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, thiazole dyes, oxazine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes.

The pigment (A1-2) is not particularly limited and any known pigment can be used. For example, pigments classified as pigments in the Color Index (published by the Society of Dyers and Colourists) can be used.
Examples of pigments classified as C.I. Pigment 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, 185, 194, 214, and 231;
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, 144, 149, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273;
blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60;
Violet pigments such as C.I. Pigment Violet 1, 19, 23, 32, 36, 38;
green pigments such as C.I. Pigment Green 7, 36, 58, 59, 62, 63;
Brown pigments such as C.I. Pigment Brown 23 and 25;
black pigments such as C.I. Pigment Black 1 and 7;

It is preferable that the colorant (A) contains at least one pigment selected from the group consisting of yellow pigments and green pigments. It is particularly preferable that the colorant (A) contains C.I. Pigment Yellow 138, 139, 185, 231, C.I. Pigment Green 7, 36, 58, 59, 62, 63.

The content of pigment (A1-2) is preferably 1 to 50 mass %, more preferably 5 to 40 mass %, and even more preferably 10 to 30 mass %, of the total amount of colorant (A).

The content of the yellow pigment or green pigment is preferably 50 to 100 mass% of the total amount of pigment, more preferably 70 to 100 mass%, even more preferably 90 to 100 mass%, and particularly preferably 100 mass%. When both a yellow pigment and a green pigment are contained, the above content refers to the total content of the yellow pigment and the green pigment.

Pigment (A1-2) may be subjected to, as necessary, rosin treatment, surface treatment using a derivative having an acidic or basic group introduced therein, grafting treatment to the pigment surface using a polymer compound, atomization treatment using sulfuric acid atomization, washing treatment using an organic solvent or water to remove impurities, removal treatment of ionic impurities using ion exchange, etc. It is preferable that the particle size of the pigment is approximately uniform. By adding a dispersant and carrying out a dispersion treatment, the pigment can be made into a pigment dispersion liquid in which the pigment is uniformly dispersed in the dispersant solution. When multiple pigments are used, each may be dispersed individually, or multiple types may be mixed and dispersed. The pigment may also be mixed with the compound (1a) and compound (1b) and then dispersed.

Examples of dispersants include surfactants, which may be cationic, anionic, nonionic, or amphoteric. Specific examples include polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. Examples of dispersants by trade name include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLORENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF), AJISPER (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.). Resin (B), which will be described later, may be used as the dispersant.

When a dispersant is used, the amount of the dispersant (solid content) used is usually 10 to 200 parts by mass, preferably 15 to 180 parts by mass, and more preferably 20 to 160 parts by mass, per 100 parts by mass of pigment. When the amount of the dispersant used is within the above range, a pigment dispersion in a more uniformly dispersed state tends to be obtained.

When a dispersant is used, the amount of the dispersant (solid content) used is preferably 1 to 500 parts by mass, more preferably 5 to 300 parts by mass, even more preferably 10 to 200 parts by mass, and even more preferably 15 to 180 parts by mass, per 100 parts by mass of compound (1a) and compound (1b). When the amount of the dispersant used is within the above range, a colored dispersion liquid in a more uniformly dispersed state tends to be obtained. When the colored resin composition contains both compound (1a) and compound (1b), 100 parts by mass of compound (1a) and compound (1b) means the total amount of these.

When a dispersant is used, the amount of the dispersant (solid content) used is usually 10 to 200 parts by mass, preferably 15 to 180 parts by mass, and more preferably 20 to 160 parts by mass, per 100 parts by mass of pigment. When the amount of the dispersant used is within the above range, a pigment dispersion in a more uniformly dispersed state tends to be obtained.

The content of colorant (A1) is preferably 1 to 50 mass% of the total amount of colorant (A), more preferably 5 to 40 mass%, and even more preferably 10 to 30 mass%.

The content of colorant (A) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, even more preferably 10 to 60% by mass, and even more preferably 12 to 55% by mass, based on the total amount of solids in the colored resin composition. When the content of colorant (A) is within the above range, the color density when made into a color filter is sufficient, and the necessary amount of resin (B) can be contained in the composition, so that a pattern with sufficient mechanical strength can be formed, which is preferable.

Here, the "total amount of solids" in this specification refers to the amount obtained by subtracting the content of organic solvent from the total amount of the colored resin composition. The total amount of solids and the content of each component relative to the total amount of solids can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]: a copolymer having a structural unit derived from at least one member (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and 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;
Resin [K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, may be referred to as "(c)");
Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
Resin [K4]: a copolymer having a structural unit derived from (a) to which (b) has been added, and a structural unit derived from (c);
Resin [K5]: a copolymer having a structural unit derived from (b) to which (a) has been added, and a structural unit derived from (c);
Resin [K6]: A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a polyvalent carboxylic acid and/or a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 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-cyclohexenedicarboxylic acid;
Bicyclounsaturated compounds containing a carboxy group, 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 acid 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 divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, etc. are preferred from the standpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkaline solution.

(b) is, for example, a polymerizable compound 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 an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms 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 a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

Examples of (b1) include monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

(b1-1) includes glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl oxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (BI) and compounds represented by formula (BII).

［式（ＢＩ）及び式（ＢＩＩ）中、Ｒ^e及びＲ^fは、水素原子、又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｘ^e及びＸ^fは、単結合、＊－Ｒ^g－、＊－Ｒ^g－Ｏ－、＊－Ｒ^g－Ｓ－又は＊－Ｒ^g－ＮＨ－を表す。
Ｒ^gは、炭素数１～６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］

In formula (BI) and formula (BII), R ^e and R ^f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.
X ^e and X ^f each represent a single bond, *-R ^g -, *-R ^g -O-, *-R ^g -S- or *-R ^g -NH-.
R ^g represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond to O.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^e and R ^f are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.
X ^e and X ^f are preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O-, and more preferably a single bond or *-CH ₂ CH ₂ -O- (* represents a bond to O).

Examples of compounds represented by formula (BI) include compounds represented by any of formulas (BI-1) to (BI-15). Among them, compounds represented by formulas (BI-1), (BI-3), (BII-5), (BI-7), (BI-9) or (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9) or (BI-15) are more preferred.

Examples of the compound represented by formula (BII) include compounds represented by any of formulas (BII-1) to (BII-15). Among them, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9) or (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9) or (BII-15) are more preferred.

The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more kinds. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the content ratio thereof (compound represented by formula (BI) : compound represented by formula (BII)) is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like.

As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

As for (b), (b1) is preferable in that it can further increase the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter. Furthermore, (b1-2) is more preferable in that the storage stability of the colored resin composition is excellent.

Examples of (c) include (meth)acrylic acid esters (cf-1) (hereinafter sometimes referred to as "cf-1")) that do not have a polycyclic hydrocarbon ring, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;
(meth)acrylic acid esters having polycyclic hydrocarbon rings (cf-2) (hereinafter sometimes referred to as "cf-2") such as tricyclo[5.2.1.0 ^2,6 ]decane-8-yl(meth)acrylate (commonly referred to as "dicyclopentanyl(meth)acrylate" in the technical field and also referred to as "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decene-8-yl(meth)acrylate (commonly referred to as "dicyclopentenyl(meth)acrylate" in the technical field), dicyclopentanyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl(meth)acrylate;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl 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, chloro[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-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene bicyclounsaturated compounds such as ene, 5-cyclohexyloxycarbonylbicyclo[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;
dicarbonyl imide 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;
Examples of the copolymer include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
Of these, (meth)acrylic acid esters are preferred.

In the resin [K1], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K1] is as follows:
Structural units derived from (a): 2 to 60 mol%
Structural units derived from (b): 40 to 98 mol%
It is preferred that
Structural units derived from (a): 10 to 50 mol %
Structural units derived from (b): 50 to 90 mol%
It is more preferable that:
When the ratio of the structural unit of the resin [K1] is within the above range, the colored resin composition tends to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the obtained color filter.

Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in said literature.

Specific examples of the method include a method in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and the atmosphere is deoxygenated by, for example, replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring. The polymerization initiator and solvent used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc.), and the solvent may be any that dissolves each monomer, such as the solvents described below as the organic solvent (C) of the colored resin composition of the present invention.

The copolymer obtained may be used as it is in the form of a solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation. In particular, by using a solvent contained in the colored resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is in the preparation of the colored resin composition of the present invention, and the manufacturing process of the colored resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K2] is as follows:
Structural units derived from (a): 2 to 45 mol%
Structural units derived from (b): 2 to 95 mol%
Structural units derived from (c): 1 to 65 mol%
It is preferred that
Structural units derived from (a): 5 to 40 mol%
Structural units derived from (b): 5 to 80 mol%
Structural units derived from (c): 5 to 60 mol%
It is more preferable that:
When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained color filter tend to be excellent.

Resin [K2] can be produced, for example, in the same manner as described for producing resin [K1].

In the resin [K3], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K3] is as follows:
Structural units derived from (a): 2 to 60 mol%
Structural units derived from (c): 40 to 98 mol%
It is preferred that
Structural units derived from (a): 10 to 50 mol %
Structural units derived from (c): 50 to 90 mol%
It is more preferable that:
Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and/or carboxylic acid anhydride contained in (a).
First, a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for resin [K3].

Next, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b).
Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air instead of nitrogen, and (b) a catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the mixture is reacted, for example, at 60 to 130° C. for 1 to 10 hours, thereby producing the resin [K4].
The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (a). By setting it within this range, the storage stability of the colored resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to be good. Since the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, (b1) is preferable as (b) used in resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.

Resin [K5] is produced in the first step by the same method as that for producing resin [K1] described above, to obtain a copolymer of (b) and (c). As in the above, the copolymer obtained may be used as it is in the form of a solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.
The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively,
Structural units derived from (b): 5 to 95 mol%
Structural units derived from (c): 5 to 95 mol%
It is preferred that
Structural units derived from (b): 10 to 90 mol%
Structural units derived from (c): 10 to 90 mol%
It is more preferable that:

Furthermore, under the same conditions as in the production method of resin [K4], resin [K5] can be obtained by reacting a cyclic ether derived from (b) contained in a copolymer of (b) and (c) with a carboxylic acid or carboxylic anhydride contained in (a).
The amount of (a) to be reacted with the copolymer is preferably 5 to 100 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) for use in resin [K5], and (b1-1) is more preferred.

Resin [K6] is a resin obtained by further reacting resin [K5] with a polycarboxylic acid and/or a carboxylic anhydride. A hydroxyl group generated by the reaction of the cyclic ether derived from (b) with the carboxylic acid or carboxylic anhydride derived from (a) is further reacted with a polycarboxylic acid and/or a carboxylic anhydride.
Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and tricarbanilic acid. Examples of the carboxylic acid anhydride include succinic anhydride, 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. The amount of the polycarboxylic acid and/or carboxylic acid anhydride used is preferably 0.05 to 1 mol, and more preferably 0.1 to 0.5 mol, per mol of the amount of (a) used. In other words, it is more preferable that resin [K6] also has a structural unit in which (a) is added to a structural unit derived from (b), in which a polyvalent carboxylic acid and/or a carboxylic acid anhydride is not added to a hydroxy group generated by the reaction of a cyclic ether derived from (b) with a carboxylic acid or a carboxylic acid anhydride derived from (a).

Resin (B) preferably includes a resin having a structural unit with an ethylenically unsaturated bond in the side chain (resin [K4], resin [K5], or resin [K6]), and more preferably includes a resin having a structural unit with a (meth)acryloyl group in the side chain.

Examples of resins having a structural unit containing a (meth)acryloyl group in the side chain include resin [K4] using a monomer (ba) (hereinafter sometimes referred to as "ba") having a (meth)acryloyl group such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-methyl-3-methacryloyloxymethyloxetane, and tetrahydrofurfuryl acrylate as (b), resin [K5] using a monomer (aa) (hereinafter sometimes referred to as "aa") having a (meth)acryloyl group such as acrylic acid, methacrylic acid, and succinic acid mono[2-(meth)acryloyloxyethyl] as (a), and resin [K6] using (aa) as (a). As a resin having a structural unit containing a (meth)acryloyl group in the side chain, resin [K6] using (aa) as (a) is preferable.

As the resin having a structural unit containing a (meth)acryloyl group in the side chain, it is more preferable to include a resin [K6] having a structural unit containing a (meth)acryloyl group in the side chain and a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b) and further adding a polycarboxylic acid and/or a carboxylic anhydride), a structural unit containing a (meth)acryloyl group in the side chain and not containing a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b)), and a structural unit derived from (c), and more preferable to include a resin [K6] having a structural unit containing a (meth)acryloyl group in the side chain and a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b) and further adding a polycarboxylic acid and/or a carboxylic anhydride), It is more preferable to include a resin [K6] having a structural unit that contains a (meth)acryloyl group in the side chain and does not contain a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b)), and a structural unit derived from (cf-1) and/or (cf-2). It is particularly preferable to include a resin [K6] having a structural unit that contains a (meth)acryloyl group in the side chain and does not contain a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b) and further adding a polycarboxylic acid and/or a carboxylic anhydride), a structural unit that contains a (meth)acryloyl group in the side chain and does not contain a carboxylic acid group derived from a polycarboxylic acid and/or a carboxylic anhydride (a structural unit obtained by adding (aa) to a structural unit derived from (b)), and a structural unit derived from (cf-1) and (cf-2).

In addition, from the viewpoint of increasing the residual film rate, it is preferable that resin (B) further contains resin [K1] in addition to a resin having a structural unit with an ethylenically unsaturated bond in a side chain (resin [K4], resin [K5], or resin [K6]).

The weight average molecular weight of resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed parts in the developer is good, and the resolution of the colored pattern tends to be improved.

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

The acid value of resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 25 to 150 mg-KOH/g, and even more preferably 30 to 130 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 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass, based on the total amount of solids in the colored resin composition (particularly the colored curable resin composition). When the content of resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved. The content of resin (B) is preferably 40 to 98% by mass, more preferably 50 to 95% by mass, even more preferably 60 to 92% by mass, and even more preferably 70 to 90% by mass, based on the total amount of solids in colorant (A) and resin (B).

<Organic Solvent (C)>
The colored resin composition may contain an organic solvent (hereinafter, sometimes referred to as organic solvent (C)). The organic solvent (C) is not particularly limited, and an organic solvent normally used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (a solvent containing OH in the molecule and not containing -O-, -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, and the like can be mentioned.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Ether solvents 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

Ether ester solvents 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, methyl 2-ethoxypropionate, Examples include ethyl oxy-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 monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

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

Aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

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

The organic solvent (C) preferably contains one or more selected from the group consisting of ether solvents, ether ester solvents, ketone solvents, and amide solvents, more preferably contains one or more selected from the group consisting of ether ester solvents, ketone solvents, and amide solvents, even more preferably contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, and N-methylpyrrolidone, even more preferably contains propylene glycol monomethyl ether acetate and/or N-methylpyrrolidone, and particularly preferably contains propylene glycol monomethyl ether acetate.

The content of the organic solvent (C) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored resin composition of the present invention. In other words, the solid content of the colored resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the organic solvent (C) 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.

The content of propylene glycol monomethyl ether acetate in the total amount of organic solvent (C) is preferably 50 to 100 mass%, more preferably 70 to 100 mass%, even more preferably 80 to 100 mass%, even more preferably 90 to 100 mass%, and particularly preferably 100 mass%.

The total content of the colorant (A), resin (B) and organic solvent (C) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and even more preferably 99 to 100% by mass, based on the total amount of the colored resin composition.

<Leveling Agent (D)>
The colored resin composition may contain a leveling agent (hereinafter, may be referred to as leveling agent (D)). Examples of the leveling agent (D) 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), F-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 AGC Co., Ltd. (formerly 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 (D) is included, the content of the leveling agent (D) is preferably 0.001 to 0.2 mass % relative to the total amount of the colored 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 (D) is within the above range, the flatness of the color filter can be improved.

The total content of the colorant (A), resin (B), organic solvent (C) and leveling agent (D) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, even more preferably 99 to 100% by mass, and most preferably 100% by mass, based on the total amount of the colored resin composition.

<Colored curable resin composition>
In the present invention, the above-mentioned colored resin composition, a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (E)), and a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (F)) are mixed to form a colored resin composition. Also included is a colored curable resin composition comprising

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

The polymerizable compound (E) 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, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tri ... Examples of the acrylates include (2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, and caprolactone modified dipentaerythritol hexa(meth)acrylate. Of these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

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

The content of the polymerizable compound (E) is preferably 1 to 65 parts by mass, more preferably 5 to 60 parts by mass, and even more preferably 10 to 55 parts by mass, per 100 parts by mass of the resin (B).

<Polymerization initiator (F)>
The polymerization initiator (F) 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 any known polymerization initiator can be used. Examples of polymerization initiators that generate active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

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

Examples of the O-acyloxime compound 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-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)phenyl]ethane-1-imine, Examples of the methyl ether ester include N-ethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine. Commercially available products such as Irgacure OXE01 and OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used. Among them, the O-acyloxime compound is preferably at least one selected from the group consisting of N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and more preferably N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine. With these O-acyloxime compounds, a color filter with high brightness tends to be obtained.

The alkylphenone compound is a compound having a partial structure represented by the following formula (d2) or a partial structure represented by the following formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of compounds having the partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used.

Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

Examples of the triazine compounds 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, and 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc.

The acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

Further examples of the polymerization initiator (F) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (F1) (especially amines) described below.

Examples of polymerization initiators that generate 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, as well as nitrobenzyl tosylates and benzoin tosylates.

As the polymerization initiator (F), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound is preferred, and a polymerization initiator containing an O-acyloxime compound is more preferred.

The content of the polymerization initiator (F) 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 (E). When the content of the polymerization initiator (F) 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 optical filter.

<Polymerization initiator aid (F1)>
The colored resin composition may contain a polymerization initiator aid (hereinafter, may be referred to as polymerization initiator aid (F1)). The polymerization initiator aid (F1) is a compound used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator, or a sensitizer. When the polymerization initiator aid (F1) is contained, it is usually used in combination with a polymerization initiator (F). Examples of the polymerization initiator aid (F1) 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 (F1) 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 (E). When the amount of the polymerization initiation aid (F1) is within this range, a colored pattern can be formed with even higher sensitivity, and the productivity of the color filter tends to improve.

<Other ingredients>
The colored resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.

<Color filters, display devices>
The present invention also includes a color filter formed from the above-mentioned colored resin composition and colored curable resin composition. Since the colored resin composition and colored curable resin composition of the present invention have a high green brightness, the color filter obtained by using the same also has a high green brightness. The color filter is useful as a filter used in a display device (e.g., a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state imaging device.

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

The colorant (A) may be prepared using the color dispersion or pigment dispersion described above. The desired colored resin composition can be prepared by mixing the remaining components with the color dispersion or pigment dispersion to a predetermined concentration.

When the dye (A1-1) is contained, the dye (A1-1) may be dissolved in advance in part or all of the organic solvent (C) to prepare a solution. It is preferable to filter the solution through a filter having a pore size of about 0.01 to 1 μm. In addition, it is preferable to filter the colored resin composition after mixing through a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>
Examples of methods for producing a colored pattern from the colored resin composition and colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among these, the photolithography method is preferred. The photolithography method is a method in which the colored resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and/or not developing. A color filter can be formed by obtaining a colored pattern or a colored coating film in this way.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with a silica-coated surface, resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate, silicon, and the above substrates on which thin films of aluminum, silver, and silver/copper/palladium alloys are formed may be used. On these substrates, other color filter layers, resin layers, transistors, circuits, and the like may be formed. A silicon substrate that has been subjected to HMDS treatment may also be used.

The formation of each color pixel by photolithography can be performed using known or conventional equipment and conditions. For example, it can be produced as follows. First, a colored resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heating and drying (pre-baking) and/or drying under reduced pressure to obtain a smooth colored composition layer. Examples of application methods include spin coating, slit coating, and slit and spin coating. When drying by heating, the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When drying under reduced pressure, it is preferably performed under a pressure of 50 to 150 Pa and at a temperature range of 20 to 25°C.

The thickness of the coloring composition layer is not particularly limited and may be appropriately selected depending on the thickness of the desired color filter.

Next, the colored composition layer is exposed to light through a photomask to form a desired colored pattern, if necessary. The pattern on the photomask is not particularly limited, and a pattern appropriate for the intended use is used. The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specific examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

It is preferable to use a reduction projection exposure device or a proximity exposure device such as a mask aligner and a stepper, since it is possible to uniformly irradiate the entire exposure surface with parallel light and to perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed.

A colored pattern is formed on the substrate by contacting the exposed colored composition layer with a developer and developing it. The unexposed portion of the colored composition layer is dissolved in the developer and removed by development. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant. The development method may be any of a paddle method, a dipping method, and a spray method. Furthermore, the substrate may be tilted at any angle during development. After development, it is preferable to wash with water.

Furthermore, it is preferable to perform post-baking on the obtained colored pattern. The post-baking temperature is preferably 80 to 250°C, more preferably 100 to 245°C, and even more preferably 180 to 240°C. The post-baking time is preferably 1 to 120 minutes, and more preferably 2 to 30 minutes.

The thickness of the coating film after post-baking is, for example, preferably 3 μm or less, and more preferably 2.0 μm or less. There is no particular lower limit to the thickness of the coating film, but it is usually 0.1 μm or more, and may be 0.5 μm or more.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

(Dye Synthesis Example 1)
According to the description of Japanese Patent No. 6206977, the following compound (I-1) was synthesized.

(Dye Synthesis Example 2)
The following compound (X-1) was synthesized according to the description of WO 2016/076028.

(Dye Synthesis Example 3)
Compound (I-2) was synthesized according to the following scheme.

Synthesis of intermediate (I-2a) In a nitrogen-substituted four-neck flask, 12.8 parts of 3-(pentafluorosulfanyl)phenylboronic acid (manufactured by Ube Industries, Ltd.), 7.00 parts of 3-chlorophthalonitrile (manufactured by Kanto Chemical Co., Ltd.), 15.7 parts of cesium fluoride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.48 parts of tris(dibenzylideneacetone)dipalladium(0) (manufactured by N.E. Chemcat Corporation), 0.53 parts of tri-tert-butylphosphonium tetrafluoroborate (manufactured by Tokyo Chemical Industry Co., Ltd.), 112 parts of 1,4-dioxane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4.3 parts of ion-exchanged water were added and stirred at 93 ° C. for 7 hours. Thereafter, the contents were cooled to room temperature, toluene was added thereto, and the mixture was stirred at room temperature for 30 minutes. Thereafter, insoluble matter was filtered, and the obtained filtrate was washed three times with ion-exchanged water. Thereafter, anhydrous magnesium sulfate was added to the obtained organic layer to dry it, and then the layer was filtered, and the obtained filtrate was concentrated. Thereafter, the obtained brown solid was washed with a mixed solvent of toluene/methanol, and then recrystallized from a mixed solvent of acetonitrile/ion-exchanged water to obtain 9.63 parts (yield 68%) of intermediate (I-2a) as a white solid.

Synthesis of Compound (I-2) 1.00 part of intermediate (I-2a) and 0.14 parts of zinc chloride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a nitrogen-substituted recovery flask, and the mixture was stirred for 1.5 hours at 220° C. Thereafter, the resulting mixture was dissolved in toluene and purified by gel permeation chromatography (gel carrier: Bio-Beads S-X3 Support, manufactured by BIO-RAD), to obtain 0.37 parts (yield 36%) of compound (I-2) as a dark green solid.

(Dye Synthesis Example 4)
Compound (I-3) was synthesized according to the following scheme.

Synthesis of intermediate (I-3a) In a nitrogen-substituted four-neck flask, 11.9 parts of 4-(pentafluorosulfanyl)phenylboronic acid (manufactured by Ube Industries, Ltd.), 6.50 parts of 3-chlorophthalonitrile, 14.6 parts of cesium fluoride, 0.45 parts of tris(dibenzylideneacetone)dipalladium(0), 0.49 parts of tri-tert-butylphosphonium tetrafluoroborate, 103 parts of 1,4-dioxane, and 4 parts of ion-exchanged water were added and stirred at 93 ° C. for 8 hours. Thereafter, the contents were cooled to room temperature, toluene was added thereto, and the mixture was stirred at room temperature for 30 minutes. Thereafter, insoluble matter was filtered, and the obtained filtrate was washed three times with ion-exchanged water. Thereafter, anhydrous magnesium sulfate was added to the obtained organic layer to dry it, and then the mixture was filtered, and the obtained filtrate was concentrated. Thereafter, the obtained brown solid was washed with a mixed solvent of toluene/methanol and then recrystallized from a mixed solvent of acetonitrile/ion-exchanged water to obtain 4.26 parts (yield 32%) of intermediate (I-3a) as a white solid.

Synthesis of Compound (I-3) In a nitrogen-purged recovery flask, 1.00 part of intermediate (I-3a) and 0.14 parts of zinc chloride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added and stirred for 1 hour at 220° C. Thereafter, the resulting mixture was cooled to room temperature and washed with methanol to obtain 0.12 parts (yield 12%) of compound (I-3) as a blue-green solid.

(Dye Synthesis Example 5)
Mixture (I-4) was synthesized according to the following scheme.

Synthesis of Mixture (I-4) In a nitrogen-substituted recovery flask, 1.00 part of intermediate (I-3a), 0.39 parts of phthalonitrile (Pn, manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.14 parts of zinc chloride were added and stirred for 1.5 hours at 220° C. Thereafter, the resulting mixture was cooled to room temperature and repeatedly washed with a mixed solvent of acetonitrile/ion-exchanged water, thereby obtaining 0.31 parts of mixture (I-4) consisting of the compound group shown in the above scheme as a dark green solid.

(Resin Synthesis Example 1)
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, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Next, a mixed solution of 38 parts of acrylic acid, 289 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 (mixing ratio 1:1) and 125 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 5 hours. Meanwhile, a mixed solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator dissolved in 235 parts of propylene glycol monomethyl ether acetate was dropped into the flask over 6 hours. After the dropwise addition was completed, the flask was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a B-type viscosity (23°C) of 125 mPa·s and a solid content of 35.1%. The weight average molecular weight Mw of the produced copolymer (polymer; resin (B-1)) was 9200, the dispersity was 2.08, and the acid value of the solid content was 77 mg-KOH/g. Resin (B-1) has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40°C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0mL/min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
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 (Mw/Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.

(Preparation of Dispersion (P-1))
12.0 parts of the compound (X-1), 4.8 parts of a dispersant (BYK-LP N 21324 manufactured by BYK Japan KK), 3.6 parts of the resin (B-1) (solid content equivalent), and 79.6 parts of propylene glycol monomethyl ether acetate as a solvent were mixed, and 300 parts of zirconia beads were added and shaken, and the zirconia beads were removed by filtration to prepare a dispersion (P-1).

[Examples 1 to 4, Comparative Example 1]
The components were mixed so as to obtain the final composition shown in Table 3 below, to obtain colored resin compositions of Examples 1 to 4 and Comparative Example 1. In Comparative Example 1, the above-mentioned dispersion liquid (P-1) was used for mixing.

In Table 3, each component represents the following compound.
Colorant (I-1): Compound represented by formula (I-1) Colorant (I-2): Compound represented by formula (I-2) Colorant (I-3): Compound represented by formula (I-3) Colorant (I-4): Compound represented by formula (I-4) Colorant (X-1): Compound represented by formula (X-1) Dispersant (A-1): Acrylic dispersant (BYK-LP N 21324, manufactured by BYK Japan)
Resin (B-1): Resin (B-1) (solid content equivalent)
Solvent (C-1): Propylene glycol monomethyl ether acetate Solvent (C-2): N-methylpyrrolidone (NMP)
Leveling agent (D-1): Polyether modified silicone oil ("Toray Silicone SH8400" manufactured by Dow Corning Toray Co., Ltd.)

<Preparation of color filter (colored coating film)>
The colored resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100° C. for 3 minutes, followed by post-baking at 230° C. for 30 minutes to obtain a colored coating film.

<Preparation Example 1>
(Preparation of yellow resin composition)
6.6 parts of C.I. Pigment Yellow 185 (Y185) which is a yellow pigment, 5.0 parts of a dispersant (BYK-LP 6919 manufactured by BYK Japan Co., Ltd.), 3.0 parts of the above resin B-1 (solid content equivalent), and 85.4 parts of propylene glycol monomethyl ether acetate as a solvent were mixed, 300 parts of zirconia beads were added, the mixture was shaken, and the zirconia beads were removed by filtration to prepare a yellow resin composition.

<Preparation Example 2>
(Preparation of green resin composition)
6.6 parts of C.I. Pigment Green 63 (G63) which is a green pigment, 6.0 parts of a dispersant (BYK-LP 21116 manufactured by BYK Japan Co., Ltd.), 5.0 parts of the above resin B-1 (solid content equivalent), and 82.4 parts of propylene glycol monomethyl ether acetate as a solvent were mixed, 300 parts of zirconia beads were added, the mixture was shaken, and the zirconia beads were removed by filtration to prepare a green resin composition.

<Measurement of transmission spectrum>
The transmission spectra of the colored coating film, the yellow resin composition, and the green resin composition were measured using a colorimeter (OSP-SP-200) manufactured by Olympus Corporation.

<Calculation of brightness>
Using the transmission spectrum obtained from the colored resin composition of the Example or Comparative Example, the transmission spectrum obtained from the yellow resin composition and the green resin composition of Preparation Examples 1 and 2, and the characteristic function of the C light source, the brightness Y at the CIE chromaticity coordinates (x, y) = (0.2550, 0.6500) was calculated as a formula. In detail, the colored resin composition of Examples 1 to 4 or Comparative Example 1 and the yellow colored resin composition were mixed (mixed by simulation) in the ratios shown in Table 4 below so as to be matched by color matching calculation by additive color mixing to obtain the CIE chromaticity coordinates (x, y) = (0.2550, 0.6500), and the brightness Y was calculated as a formula. Similarly, the colored resin compositions of Examples 1 to 4 and Comparative Example 1, the yellow colored resin composition, and the green colored resin composition were mixed (by simulation) in the ratios shown in Table 4 below so that the CIE chromaticity coordinates were (x, y) = (0.2550, 0.6500), to give Examples 5 to 8 and Comparative Example 2, and the brightness Y was calculated using the formula. A larger Y value indicates a higher brightness.

[Example 9, Comparative Example 3]
The colored curable resin compositions of Example 9 and Comparative Example 3 are obtained by adding the polymerizable compound (E) and the polymerization initiator (F) to the colored resin compositions of Example 1 and Comparative Example 1 in Table 3 above. The colored curable resin composition is applied by spin coating onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated), pre-baked at 100° C. for 3 minutes, and then post-baked at 230° C. for 30 minutes to obtain a colored coating film having a similar brightness in the same CIE chromaticity coordinates.

The colored resin composition of the present invention can form a color filter with a high green brightness.

Claims (7)

Contains a colorant and a resin,
A colored resin composition, characterized in that the colorant comprises a phthalocyanine compound in which one or more hydrogen atoms are substituted with _SF5 . The colored resin composition according to claim 1 , wherein the colorant comprises a compound represented by the following formula (1a) and/or (1b):

[In formula (1a) and formula (1b),
R ^x 's each independently represent SF ₅ or a hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with SF ₅ ;
m represents an integer from 1 to 16;
R ^y each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent;
n represents an integer from 0 to 15;
M represents a metal element which may have a substituent, or a metalloid element which may have a substituent,
The —CH ₂ — in the hydrocarbon group represented by R ^x and R ^y may be replaced by —O—, —S—, —SO ₂ —, —NH—, —CO—, or —CO ₂ —.] The compound represented by formula (1a) is a compound represented by the following formula (2a), and the compound represented by formula (1b) is a compound represented by the following formula (2b). The colored resin composition according to claim 2.

[In formula (2a) and formula (2b), R ^x , R ^y and M each have the same meaning as defined above,
o represents an integer of 1 to 4;
p represents an integer of 0 to 3. The colored resin composition according to any one of claims 1 to 3, wherein the colorant contains at least one pigment selected from the group consisting of yellow pigments and green pigments. A colored curable resin composition comprising the colored resin composition according to any one of claims 1 to 4, a polymerizable compound, and a polymerization initiator. A color filter formed from the colored curable resin composition according to claim 5. A display device including the color filter according to claim 6.