KR20170074208A - Novel compound and colored photosensitive resin composition - Google Patents

Abstract

The present invention relates to a novel salt forming compound and a colored curable resin composition represented by formula (AI), which can provide a color filter excellent in heat resistance. In the formulas, the ring Z ¹ and the ring Z ² independently represent a heterocyclic group which may have a substituent or an aromatic ring which may have a substituent, and the ring Z ¹ and / or the ring Z ² have an onium nitrogen atom . R ^a1 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. X ^{a1 -} represents an anion containing at least one element selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions and tungsten, molybdenum, silicon and phosphorus as essential elements. a1 represents an integer of 1 to 20; n is defined to be equal to the positive charge caused by the onionized nitrogen atom of ring Z < ^{1 >} and / or ring Z < ² >.

Description

NOVEL COMPOUND AND COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a novel compound and a colored curable resin composition.

Patent Document 1 discloses a salt-forming compound comprising a triarylmethane-based basic dye and an opposite compound.

Japanese Unexamined Patent Application Publication No. 2014-170098

The triarylmethane-based compound described in Patent Document 1 has already been subjected to various studies on heat resistance and the like, but studies on heat resistance can not be said to be sufficient for other compounds.

The present invention includes the following inventions.

[1] A compound represented by the formula (A-I).

≪ Formula 1 >

[In the formula (A-I)

The ring Z ¹ and the ring Z ² independently represent a heterocyclic ring which may have a substituent or an aromatic ring which may have a substituent, and the ring Z ¹ and / or the ring Z ² have an onionized nitrogen atom.

R ^a1 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted.

R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

X ^{a1 -} represents an anion containing at least one element selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions and tungsten, molybdenum, silicon and phosphorus as essential elements.

a1 represents an integer of 1 to 20;

n is defined to be equal to the positive charge caused by the onionized nitrogen atom of ring Z < ^{1 >} and / or ring Z < ^{2 &}

[2] The compound represented by the above formula (A-I) in the above [1] is a compound represented by the formula (A-II) or a compound represented by the formula (A-III).

(2)

(3)

[In the formula (A-II), R ^a1 , X ^{a1 -} and a1 have the same meanings as described in [1] above.

The ring Z ³ and the ring Z ⁴ independently represent an aromatic ring which may have a substituent.

R ^a10 and R ^a11 independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms and may have a substituent.

R ^a12 and R ^a13 independently represent a hydrogen atom, a halogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or one R ^a12 and one R ^a13 bond to each other to form a ring having 2 to 6 carbon atoms Represents a divalent aliphatic hydrocarbon group.

p1 and p2 represent an integer of 0 to 2;

In the formula (A-III), R ^a1 , X ^{a1 -} and a1 have the same meanings as described in [1] above.

R ^a20 to R ^a23 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and may have a substituent.

R ^a24 to R ^a27 independently represent a hydrogen atom, a hydroxy group, a mercapto group, a trifluoromethyl group or -NHCO-R ^a32 .

R ^a28 to R ^a31 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the hydrocarbon group may be ^replaced by -O-, -S-, -N (R ^a33 ) -, It may be substituted with -CO- or - -SO _2. However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted.

R ^a20 and R ^a24 , R ^a21 and R ^a25 , R ^a22 and R ^a26 , R ^a23 and R ^a27 each may form a ring together with the carbon atoms to which they are bonded.

R ^a20 and R ^a28 , R ^a21 and R ^a29 , R ^a22 and R ^a30 , R ^a23 and R ^a31 may form a ring together with the nitrogen atom and the carbon atom to which they are bonded, respectively.

R ^a28 and R ^a29 , R ^a30 and R ^a31 may form a ring together with the nitrogen atom to which they are bonded.

R ^a32 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the saturated hydrocarbon group may be ^replaced by -O-, -S-, -N (R ^a34 ) -, -SO ₂ - -CO-. ≪ / RTI > However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted.

R ^a33 and R ^a34 are each independently, represent a hydrogen atom, an aralkyl group having from 1 to 20 carbon atoms or a saturated hydrocarbon group having a carbon number of 7-10 with each other.]

[3] In the above [2], the ring Z ³ and the ring Z ⁴ in the formula (A-II) independently represent a phenyl group which may have a substituent,

R ^a10 and R ^a11 independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,

R ^a12 and R ^a13 independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent,

and p1 and p2 represent 2.

[4] In the above [1] to [3], wherein X ^{a1 -} it is an anion containing at least one element and oxygen is selected from the group consisting of fluorine-containing anion, or tungsten, molybdenum, silicon and phosphorus as essential elements compound.

[5] The compound according to any one of [1] to [4], wherein R ^a1 is an unsubstituted saturated hydrocarbon group having 1 to 20 carbon atoms.

[6] A colored dispersion comprising a compound according to any one of [1] to [5] and a solvent (E).

[7] A colored curable resin composition comprising a compound according to any one of [1] to [5], a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E).

[8] A color filter formed from the colored curable resin composition according to [7] above.

[9] A display device comprising the color filter described in the above [8].

It is possible to form a color filter having good heat resistance in a colored curable resin composition containing the novel compound of the present invention.

The compound of the present invention is a compound represented by the formula (A-I) (hereinafter referred to as a compound (A-I)). In the present specification, the invention is described with a compound having a specific resonance structure, but the resonance structure includes all other resonance structures.

≪ Formula 4 >

[In the formula (A-1)

The ring Z ¹ and the ring Z ² independently represent a heterocyclic ring which may have a substituent or an aromatic ring which may have a substituent, and the ring Z ¹ and / or the ring Z ² have an onionized nitrogen atom.

R ^a1 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted.

R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

X ^{a1 -} represents an anion containing at least one element selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions and tungsten, molybdenum, silicon and phosphorus as essential elements.

a1 represents an integer of 1 to 20;

n is defined to be equal to the positive charge caused by the onionized nitrogen atom of ring Z < ^{1 >} and / or ring Z < ^{2 &}

The heterocycle represented by the ring Z ¹ and the ring Z ² includes at least one heteroatom as a constituent of the ring, and may be monocyclic or polycyclic.

The hetero atom may be an atom selected from the group 15 or group 16 elements in the periodic table, and may be a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom.

Examples of the heterocyclic ring include an indole ring, a benzoindole ring, an indolenine ring, a benzoindolenine ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzoimidazole ring and a quinoline ring And a heterocyclic ring having 2 to 8 carbon atoms.

Examples of the aromatic ring represented by the ring Z ¹ and the ring Z ² include an aromatic ring having 6 to 12 carbon atoms such as a phenyl group and a naphthyl group.

As the substituent which the heterocycle or aromatic ring represented by the ring Z ¹ and the ring Z ² may have, there may be mentioned

Examples of the alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, An aliphatic hydrocarbon group;

An aryl group having 6 to 12 carbon atoms such as a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, an o-cumenyl group, ;

An aralkyl group having 7 to 10 carbon atoms such as a benzyl group;

An alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy;

An aryloxy group having 6 to 10 carbon atoms such as a phenoxy group;

An aralkyloxy group having 7 to 10 carbon atoms such as a benzyloxy group;

A group having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group;

An alkylsulfamoyl group such as methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, an alkylsulfamoyl group having 1 to 8 carbon atoms such as an n-butylsulfamoyl group, a di-n-butylsulfamoyl group and a 2-ethylhexylsulfamoyl group;

An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, an isobutylsulfonyl group, a sec-butylsulfonyl group and a tert-butylsulfonyl group;

A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom;

3-en-2-yl group, but-3-en-3-yl group, and penta-4- An alkenyl group having 2 to 6 carbon atoms such as an en-1-yl group;

A nitro group; And cyano group.

When the substituent has a hydrogen atom, the hydrogen atom may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy; An aryloxy group such as a phenoxy group and a benzyloxy group; A carboxy group; Cyano; A nitro group; Acryloyloxy group; Methacryloyloxy group and the like.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, A straight chain alkyl group having 1 to 20 carbon atoms such as an acyl group; Branched chain alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

The substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 may have is a halogen atom.

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

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

Examples of the group in which -CH ₂ - contained in the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 are substituted with -O- include the following (* indicates a bonding hand).

≪ Formula 5 >

Examples of the group in which -CH ₂ - contained in the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 are substituted with -CO- include the following (* indicates a bonding hand).

(6)

Examples of the group in which -CH ₂ - included in the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 are substituted with -NR ¹¹ - include the following (* indicates bonding loss).

≪ Formula 7 >

The -CH ₂ groups include saturated hydrocarbons having 1 to 20 carbon atoms represented by R ^a1 - a group substituted with an -OCO- include those of the following (* represents a binding hand).

(8)

Examples of the group in which -CH ₂ - included in the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 are substituted with -COO- include the following (* indicates bonding loss).

≪ Formula 9 >

The -CH ₂ groups include saturated hydrocarbons having 1 to 20 carbon atoms represented by R ^a1 - a group substituted by a -OCONH- include those of the following (* represents a binding hand).

≪ Formula 10 >

The groups in which -CH ₂ - included in the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 are substituted with -NHCOO- include the following (* indicates bonding loss).

≪ Formula 11 >

Examples of the group in which -CH ₂ - included in the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 are substituted with -CONH- include the following (* indicates binding loss).

≪ Formula 12 >

Examples of the group in which -CH ₂ - included in the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a1 are substituted with -NHCO- include the following (* indicates binding loss).

≪ Formula 13 >

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ includes a group such as R ^a1 , and among these, a methyl group is preferable.

Examples of the aralkyl group having 7 to 10 carbon atoms represented by R < ¹¹ > include a benzyl group, a phenylethyl group and a phenylbutyl group.

As R ^a1, an unsubstituted saturated hydrocarbon group of 1 to 20 carbon atoms is preferable, an unsubstituted saturated hydrocarbon group of 1 to 10 carbon atoms is more preferable, and an unsubstituted saturated hydrocarbon group of 1 to 5 carbon atoms is more preferable, and a methyl group, And propyl groups are particularly preferred.

The boron-containing anion in X ^a1 means an anion containing a boron atom.

The aluminum-containing anion in X ^a1 means an anion containing an aluminum atom.

The fluorine-containing anion in X ^a1 means an anion containing a fluorine atom.

Examples of the boron-containing anion and aluminum-containing anion include anions represented by the formula (4).

≪ Formula 14 >

[In the formula (4), W ¹ and W ² independently represent a group having two substituents formed by releasing a proton from a monovalent proton donor substituent. And M represents boron or aluminum.

Examples of the group having two substituents formed by releasing a proton from a monovalent proton donative substituent include a proton substituent group in each of two proton donating substituents from a compound having at least two monovalent proton substituents (for example, a hydroxy group, a carboxyl group, etc.) And the like. Examples of the group-linking compound include catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, 3-hydride which may have a substituent 2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, Salicylic acid, benzylic acid which may have a substituent, and mandelic acid which may have a substituent.

Examples of the substituent of the above exemplified compound include a saturated hydrocarbon group (e.g., an alkyl group, a cycloalkyl group, etc.), a halogen atom, a haloalkyl group, a hydroxyl group, an amino group, a nitro group and an alkoxy group.

Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, Monoaminosalicylic acids such as salicylic acid, 3-amino salicylic acid, 4-amino salicylic acid, 5-amino salicylic acid and 6-amino salicylic acid; (2, 4-hydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), and 6-hydroxy Monohydroxysalicylic acid such as salicylic acid (2,6-dihydroxybenzoic acid); Dihydroxysalicylic acid such as 4,5-dihydroxysalicylic acid and 4, 6-dihydroxysalicylic acid; Monohalosilicic acid such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid and 6-bromosalicylic acid; Dihalosalicylic acids such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid and 3,5-diiodo salicylic acid; Trihalosalicylic acid such as 3,5,6-trichlorosalicylic acid; And the like.

Examples of the benzylic acid which may have a substituent include benzylic acid and the like described below.

≪ Formula 15 >

Examples of the mandelic acid which may have a substituent include mandelic acid described below.

≪ Formula 16 >

The anion represented by the formula (4-1) is preferably an anion represented by the formula (4).

≪ Formula 17 >

R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ independently represent a hydrogen atom, a hydroxy group, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, Alkoxy group].

Examples of the halogen atom represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec- .

Examples of the haloalkyl group having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a tetrafluoroethyl group, a tetrachloroethyl group and a tetrabromoethyl group And the like.

Examples of the alkoxy having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, - butoxy group.

Specifically, anions represented by the anion (BC-1) to anion (BC-24), the formula (BC-25), the anion represented by the formula (BC-26) An anion represented by the formula (BC-28) and an anion represented by the formula (BC-28). In Table 1, tBu represents a tert-butyl group.

≪ Formula 18 >

(19)

(20)

≪ Formula 21 >

Anions represented by the formula (4) include anions represented by anions (BC-1), anions (BC-2), anions (BC-3) and (BC-25) (BC-1), anion (BC-2) and anion (BC-25) are more preferable, and the anion (BC- 1) and the anion (BC-2) are more preferable.

Examples of the fluorine-containing anion include an anion represented by the formula (6), an anion represented by the formula (7), an anion represented by the formula (8), and an anion represented by the formula (9).

(22)

[W ³ and W ⁴ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms, or W ³ and W ⁴ together represent an alkanediyl fluoride group having 1 to 4 carbon atoms]

≪ Formula 23 >

[W ⁵ , W ⁶ and W ⁷ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms]

≪ EMI ID =

[Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms]

≪ Formula 25 >

[Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms]

The fluorinated alkyl group having 1 to 4 carbon atoms represented by W ³ , W ⁴ , W ⁵ , W ⁶ and W ⁷ is preferably a perfluoroalkyl group. As in the perfluoroalkyl group is _{-CF 3, -CF 2 CF 3,} -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3 _), and the like _2, and -C (CF _{3) 3.}

As the fluorinated alkanediyl group having 1 to 4 carbon atoms in the formulas (6) and (8), a perfluoroalkanediyl group is preferable and -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ - , -C (CF ₃ ) ₂ -, and -CF ₂ CF ₂ CF ₂ CF ₂ -.

The anion represented by the formula (6) (hereinafter referred to as the "anion 6") is an anion represented by the formulas (6-1) to (6-6) (6-6) ").

(26)

The anion represented by the formula (7) (hereinafter referred to as the "anion (7)") is an anion represented by the formula (7-1).

≪ Formula 27 >

The anion represented by the formula (8) (hereinafter referred to as the "anion (8)") is anion represented by the formulas (8-1) to (8-4) 8-4) ").

The anion represented by the formula (9) (hereinafter referred to as the "anion (9)") is anion represented by the formulas (9-1) to (9-4) 9-4) ").

(29)

The anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements is preferably an anion of heteropoly acid or isopoly acid containing tungsten as an essential element, and is preferably an anion of tungstic acid, More preferably an anion of silicon tungstic acid and tungsten isopoly acid.

Examples of the anions of heteropoly acids or isopoly acids containing tungsten as essential elements include tungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , taurate type tungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^{6 -} , [beta] ^- [P ₂ W ₁₈ O ₆₂ ] ^6- , quadratic silicon tungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4, is in this example, with other [P ₂ W ₁₇ O _61] ^10-, [P ₂ W ₁₅ O _56] ^12-, [H ₂ W ₁₂ O ₄₈ P _2] ^12-, [NaP ₅ W ^{_{30 O 110] 14-, α- [}} SiW 9 O 34] 10-, γ- [SiW 10 O 36] 8-, α- [SiW 11 O 39] 8-, β- [SiW 11 O 39] 8- , [W ₆ O ₁₉ ] ^{2 -} , [W ₁₀ O ₃₂ ] ^{4 -} , WO ₄ ^2- and mixtures thereof.

Xa ^{1 -} is preferably an anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen.

As an anion consisting of at least one element and oxygen, selected from the group consisting of silicon and a is SiO ₃ ^{2 -} a and PO ₄ ^3-.

From the viewpoints of synthesis and post-treatment, phosphorus tungstate anion such as tungstate ion and tungstate ion, which are in the form of keel type; Silicon tungstate anion such as quasiline silicon tungstate ion; And [W ₁₀ O ₃₂ ] ⁴ -is preferred. Particularly preferred are tungstic acid anion and tungsten-based isopoly acid anion.

a1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 6.

The compound (A-I) is preferably a compound represented by the formula (A-II) or the formula (A-III).

(30)

[In the formula (A-II), R ^a1 , X ^{a1 -} and a1 have the same meanings as above.

The ring Z ³ and the ring Z ⁴ independently represent an aromatic ring which may have a substituent.

R ^a10 and R ^a11 independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms and may have a substituent.

R ^a12 and R ^a13 independently represent a hydrogen atom, a halogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or one R ^a12 and one R ^a13 bond to each other to form a ring having 2 to 6 carbon atoms Represents a divalent aliphatic hydrocarbon group.

p1 and p2 represent an integer of 0 to 2.]

Examples of the substituent that the aromatic ring represented by the ring Z ³ and the ring Z ⁴ may have include the same substituent that the aromatic ring represented by the ring Z ¹ and the ring Z ² may have.

Examples of the substituents of the ring Z ³ and the ring Z ⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, An aliphatic hydrocarbon group having 1 to 6 carbon atoms such as a tert-pentyl group;

A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom;

An aliphatic hydrocarbon group of 1 to 6 carbon atoms substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; .

When the ring Z ³ and the ring Z ⁴ are phenyl groups, those having a substituent at the 5th and / or 6th position in the formula (Z ³ -N) and the formula (Z ⁴ -N) are preferred, and those having a substituent at the 5th position are more preferable Do.

(31)

R ^a10 And the aliphatic hydrocarbon group having 1 to 20 carbon atoms for R ^a11 include monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms as exemplified for R ^a1 ; An unsaturated hydrocarbon group having 1 to 20 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a 3-methyl-butenyl group, a 4-methyl-pentenyl group and a 5-methyl- And the like. Among them, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable, an aliphatic hydrocarbon group having 1 to 5 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group or a butyl group is more preferable. The aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably unsubstituted or substituted with a halogen atom (more preferably a chlorine atom or a fluorine atom).

-CH ₂ - included in the aliphatic hydrocarbon group is substituted with -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- . However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted. R ¹¹ is the same as above.

Examples of the aromatic hydrocarbon group represented by R ^a10 and R ^a11 include an aryl group having 6 to 18 carbon atoms such as a phenyl group and a naphthyl group; And an aralkyl group having 7 to 18 carbon atoms such as a benzyl group.

^{Examples of} the substituent which the aromatic hydrocarbon group represented by R ^a10 and R ^a11 may have include a halogen atom such as a fluorine atom, a chlorine atom and iodine; An alkoxy group having 1 to 6 carbon atoms such as methoxy and ethoxy; A hydroxy group; An alkyl group having 1 to 6 carbon atoms such as methyl group and ethyl group; A sulfamoyl group; An alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; And alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group.

As the aromatic hydrocarbon group which may be substituted, there may be mentioned a group represented by the following formula. In the following formula, * denotes a binding hand. Specific examples of the aralkyl group which may be substituted include groups in which -CH ₂ - is bonded to the bond of each of the following aromatic hydrocarbon groups.

(32)

≪ Formula 33 >

(34)

^Examples of the halogen atom of R ^a12 and R ^a13 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom.

The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by R ^a12 and R ^a13 may be any one of an alkyl group, an alkenyl group and an alkynyl group, preferably an alkyl group, and may be any of linear, branched or cyclic.

^Examples of the straight chain or branched chain aliphatic hydrocarbon group of R ^a12 and R ^a13 include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- ; A methyl group, an ethyl group, a propyl group, an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, Ethyl group, a 2-ethyl-2-methylpropyl group, a branched heptyl group, a tert-butyl group, Branched chain alkyl groups such as a t-butyl group and a 1-methylheptyl group; And a chain alkenyl group such as a propenyl group and a hexenyl group.

^Examples of the cyclic aliphatic hydrocarbon group of R ^a12 and R ^a13 include monocyclic cycloalkyl groups such as cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group and cyclohexyl group.

Examples of the substituent which the aliphatic hydrocarbon group of R ^a12 and R ^a13 may have include an aryl group (for example, a carbon number of 6 to 10), an alkyloxy group (for example, a carbon number of 1 to 10), an aryloxy group (For example, 2 to 10 carbon atoms), an aminocarbonyl group, a hydroxy group, a cyano group, etc. may be substituted with a halogen atom, an acyloxy group, an acyloxy group, .

One R ^a12 and one R ^a13 may combine with each other to represent a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms. Examples of the divalent aliphatic hydrocarbon group include straight, branched or cyclic aliphatic hydrocarbon groups such as a methylene group, an ethylene group, A straight chain alkylene group; A branched alkylene group such as an isopropylene group and a branched butylene group; And the like.

p1 and p2 represent an integer of 0 to 2, preferably 1 or 2, and more preferably 2.

≪ Formula (A-III) >

≪ Formula 35 >

[In the formula (A-III), R ^a1 , X ^{a1 -} and a1 have the same meanings as above.

R ^a20 to R ^a23 independently represent a hydrogen atom, a halogen atom, a hydroxy group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a saturated hydrocarbon group having 1 to 20 carbon atoms and may have a substituent.

R ^a24 to R ^a27 independently represent a hydrogen atom, a hydroxy group, a mercapto group, a trifluoromethyl group or -NHCO-R ^a32 .

R ^a28 to R ^a31 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the hydrocarbon group is -O-, -S-, -N (R ^a33 ) -, It may be substituted with -CO- or - -SO _2. However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted.

R ^a20 and R ^a24 , R ^a21 and R ^a25 , R ^a22 and R ^a26 , R ^a23 and R ^a27 each may form a ring together with the carbon atoms to which they are bonded.

R ^a20 and R ^a28 , R ^a21 and R ^a29 , R ^a22 and R ^a30 , R ^a23 and R ^a31 may form a ring together with the nitrogen atom and the carbon atom to which they are bonded, respectively.

R ^a28 and R ^a29 , R ^a30 and R ^a31 may form a ring together with the nitrogen atom to which they are bonded.

R ^a32 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - which constitutes the monovalent saturated hydrocarbon group may be ^replaced by -O-, -S-, -N (R ^a34 ) -, -SO ₂ - or -CO-. ≪ / RTI > However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted.

R ^a33 and R ^a34 are each independently, represent a hydrogen atom, an aralkyl group having from 1 to 20 carbon atoms or a saturated hydrocarbon group having a carbon number of 7-10 with each other.]

^Examples of the halogen atom represented by R ^a20 to R ^a23 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The aromatic hydrocarbon which may have a substituent represented by R ^a20 to R ^a23 preferably has 6 to 10 carbon atoms.

^Examples of the substituent capable of substituting the aromatic hydrocarbon group represented by R ^a20 to R ^a23 include an alkenyl group having 1 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group; An alkyloxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group; A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; A haloalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; And the like.

^Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^a20 to R ^a23 include an aryl group such as phenyl, tolyl, xylyl, mesityl, cumenyl, biphenyl, naphthyl, anthryl and phenanthryl; An aralkyl group such as a benzyl group, a phenylethyl group and a phenylbutyl group; An aryloxy group such as a phenoxy group; An aralkyloxy group such as a benzyloxy group; And the like.

The number of carbon atoms of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a20 to R ^a23 is preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 8, still more preferably 1 to 7 to be. Specific examples of the saturated hydrocarbon group include a saturated hydrocarbon group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, A straight chain alkyl group having from 20 to 20 carbon atoms; Branched chain alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 1-ethylpentyl and 2-ethylhexyl; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

R ^a20 and R ^a24 , R ^a21 and R ^a25 , R ^a22 and R ^a26 , R ^a23 and R ^a27 each may form a ring together with the carbon atoms to which they are bonded. Examples of the ring include structures represented by the following formulas. In the formula, R ^A1 represents the same group as R ^a20 to R ^a23 , R ^A2 represents the same group as R ^a24 to R ^a27, and R ^A3 represents the same group as R ^a28 to R ^a31 . * Indicates a combined hand.

≪ EMI ID =

R ^a20 and R ^a28 , R ^a21 and R ^a29 , R ^a22 and R ^a30 , R ^a23 and R ^a31 each may form a ring together with the nitrogen atom and the carbon atom to which they are bonded. Examples of the ring include structures represented by the following formulas. In the formula, R ^A1 represents the same group as R ^a20 to R ^a23 , R ^A2 represents the same group as R ^a24 to R ^a27, and R ^A3 represents the same group as R ^a28 to R ^a31 . * Indicates a combined hand.

(37)

R ^a24 to R ^a27 independently represent a hydrogen atom, a hydroxy group, a mercapto group, a trifluoromethyl group or -NHCO-R ^a32 .

R ^a32 represents a saturated hydrocarbon group of 1 to 20 carbon atoms, preferably a saturated hydrocarbon group of 1 to 8 carbon atoms, more preferably a saturated hydrocarbon group of 1 to 4 carbon atoms.

-CH ₂ - constituting a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms of R ^a32 may be substituted with -O-, -S-, -N (R ^a34 ) -, -SO ₂ - or -CO-. However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted.

The hydrogen atom contained in the monovalent saturated hydrocarbon group of R ^a32 may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxyl group or an amino group. Details will be described later.

R ^a34 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. R ^a34 is preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, and still more preferably a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms.

The hydrocarbon group of R ^a28 to R ^a31 is preferably an aromatic hydrocarbon group having 8 to 20 carbon atoms, a saturated hydrocarbon group having 1 to 20 carbon atoms, and an unsaturated hydrocarbon group having 1 to 20 carbon atoms. The substituent of the hydrocarbon group is preferably an aliphatic hydrocarbon group (preferably an alkyl group or an alkenyl group) having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms).

The aromatic hydrocarbon group having 8 to 20 carbon atoms of R ^a28 to R ^a31 preferably has a carbon number of 18 or less, more preferably 15 or less.

The aromatic hydrocarbon group represented by R ^a28 to R ^a31 is preferably an aryl group having 8 to 12 carbon atoms and an aralkyl group having 8 to 12 carbon atoms. The aryl group is more preferably a phenyl group, and the aralkyl group is more preferably a benzyl group. The aryl group preferably has a substituent at the ortho position of the bonding hand, and the aralkyl group preferably has a substituent at the ortho position of the alkylene group. Specific examples of the aromatic hydrocarbon group represented by R ^a28 to R ^a31 include groups represented by the following formulas. In the formula, * denotes a combined hand.

≪ Formula 38 >

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a28 to R ^a31 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, A straight chain alkyl group having 1 to 20 carbon atoms such as an eicosyl group; Branched chain alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group; .

Examples of the unsaturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a28 to R ^a31 include vinyl, propenyl, butenyl, pentenyl, hexenyl, 3-methyl- Monovalent unsaturated hydrocarbon groups of 1 to 20 carbon atoms such as a decyl group, a decyl group, a decenyl group, a decenyl group, a hexadecenyl group and an icosenyl group; And the like.

R ^a28 and R ^a29 , R ^a30 and R ^a31 may form a ring together with the nitrogen atom to which they are bonded. Examples of the ring include structures represented by the following formulas.

≪ EMI ID =

The saturated hydrocarbon group of R ^a28 to R ^a31 or -CH ₂ - constituting the unsaturated hydrocarbon group may be substituted with -O-, -S-, -N (R ^a33 ) -, -SO ₂ - or -CO-. However, adjacent -CH ₂ - can not be substituted with a same group at the same time, and -CH ₂ - at the terminal can not be substituted.

The hydrogen atom contained in the monovalent saturated hydrocarbon group of R ^a28 to R ^a31 may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxyl group or an amino group.

R ^a33 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. As R ^a33 , a saturated hydrocarbon group having 1 to 20 carbon atoms is preferable, a saturated hydrocarbon group having 1 to 8 carbon atoms is more preferable, and a saturated hydrocarbon group having 1 to 4 carbon atoms is more preferable.

-CH ₂ - constituting the saturated hydrocarbon group of R ^a28 to R ^a32 is substituted with -O-, -S-, -N (R ^a33 ) -, -N (R ^a34 ) -, -SO ₂ - or -CO- A group substituted by a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a hydroxy group or an amino group in the saturated hydrocarbon group is preferably a group in which -CH ₂ - constituting a saturated hydrocarbon group is -O-, A group in which at least one of -S-, -N (R ^a33 ) -, -N (R ^a34 ) -, -SO ₂ - and -CO- is substituted or a hydrogen atom contained in a saturated hydrocarbon group is substituted with a halogen atom Or a combination thereof may be used.

Examples of the group in which -CH ₂ - constituting the saturated hydrocarbon group is substituted with -O- include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- An alkyloxy group such as a pentyloxy group; .

Examples of the group in which -CH ₂ - constituting the saturated hydrocarbon group is substituted with -O- and -CO- include alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group; An alkylcarbonyloxy group such as an acetoxy group; An arylcarbonyloxy group such as a benzoyloxy group; And the like.

Further, the groups substituted with -CH ₂ -, -N (R ^a33 ) -, -N (R ^a34 ) - and -CO- constituting the saturated hydrocarbon group include N-methylcarbamoyl group, N-ethylcarbamoyl group, N An N-isopropylcarbamoyl group, an N-isopropylcarbamoyl group, an N-isobutylcarbamoyl group, an N-sec-butylcarbamoyl group, an N-tert- Carbamoyl group, N- (1-ethylpropyl) carbamoyl group, N- (1,1-dimethylpropyl) carbamoyl group, N- (1-methylbutyl) carbamoyl group, N- (2-methylbutyl) carbamoyl group, N- (3-methylbutyl) carbamoyl group, N-cyclopentylcarbamoyl group, N-hexylcarbamoyl group, N- (1,3-dimethylbutyl) carbamoyl group, N- (3,3-dimethylbutyl) carbamoyl group, N- Hexyl) carbamoyl group, N- (1,4-dimethylpentyl) carbamoyl group, N-octylcarbamoyl group, N- (2-ethylhexyl) Carbamoyl group, N- (1,5- dimethyl-hexyl) carbamoyl and N- (1,1,2,2- tetramethylbutyl) carboxamide N-1-substituted carbamoyl group such as carbamoyl group;

An N, N-diethylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-dimethylcarbamoyl group, (1-methylpropyl) carbamoyl group, an N, N-heptylmethylcarbamoyl group and an N, N-heptylmethylcarbamoyl group, An N, N-2-substituted carbamoyl group such as a bis (2-ethylhexyl) carbamoyl group; And the like.

A -SO ₂ - - -CH ₂ constituting a saturated hydrocarbon, -N (R ^a33) -, and -N (R ^a34) - group is a N- methyl-sulfamoyl, N- ethyl-sulfamoyl, N-substituted by Butylsulfamoyl group, N-isopropylsulfamoyl group, N-isopropylsulfamoyl group, N-isopropylsulfamoyl group, N-isobutylsulfamoyl group, N-sec- A sulfamoyl group, an N- (1-ethylpropyl) sulfamoyl group, an N- (1,1-dimethylpropyl) sulfamoyl group, (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- Hexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) A moiety and a N- (1,1,2,2-tetramethyl Butyl) sulfamoyl N-1 substituted sulfamoyl group such as a parent group;

An N, N-dimethylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N, N-ethylmethylsulfamoyl group, (1-methylpropyl) sulfamoyl group, an N, N-heptylmethylsulfamoyl group and an N, N-heptylmethylsulfamoyl group, N, N-2 substituted sulfamoyl groups such as bis (2-ethylhexyl) sulfamoyl group;

And the like.

Is ^{-N (R a33) - - -CH} 2 constituting a saturated hydrocarbon, -N (R ^a34) - a group is substituted with N- methylamino group, N- ethylamino group, N- propylamino group, N- isopropyl-amino group , N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group, N- (1-ethylpropyl) amino group, N- ) Amino group, N- (2-methylbutyl) amino group, N- (2-methylpropyl) amino group, N- (3-methylbutyl) amino group, N-cyclopentylamino group, N-hexylamino group, N- (1,3- (1-methylhexyl) amino group, N- (1,4-dimethylpentyl) amino group, N-octylamino group, N- , 1,2,2-tetramethylbutyl) amino group;

N, N-diethylamino group, N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, N, N-dialkylamino groups such as N, N-butylethylamino group, N, N-bis (1-methylpropyl) amino group, N, N-heptylmethylamino group and N, ;

N-tert-butylaminomethyl group, N-tert-butylaminomethyl group, N-tert-butylaminomethyl group, N-isopropylaminomethyl group, (1, 2-dimethylpropyl) aminomethyl group, N- (1,1-dimethylpropyl) aminomethyl group, N- (2-methylbutyl) aminomethyl group, N- (3-methylbutyl) aminomethyl group, N-cyclopentylaminomethyl group, N- (1-methylbutyl) aminomethyl group, N- (3,3-dimethylbutyl) aminomethyl group, N-heptylaminomethyl group, N- - (1,4-dimethylpentyl) aminomethyl group, N-octylaminomethyl group, N- (2-ethylhexyl) aminomethyl group, N- (1,5- , 2-tetramethylbutyl) aminomethyl group and the like An N-alkylaminomethyl group;

An N, N-dimethylaminomethyl group, an N, N-ethylmethylaminomethyl group, an N, N-diethylaminomethyl group, (1-methylpropyl) aminomethyl group, N, N-heptylmethylaminomethyl group and N, N-bis (2-ethylhexyl) amino N, N-dialkylaminomethyl groups such as methyl group;

And the like.

Examples of the group in which the hydrogen atom contained in the saturated hydrocarbon group is substituted with a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoro (isopropyl) group, a perfluoro (isopropenyl) group, A perfluoro (butyl group), a perfluoro (sec-butyl) group, a perfluoro (tert-butyl) group, a perfluoro (2-butenyl) group, a perfluoro (1,3-butadienyl) group, a perfluoropentyl group, a perfluoro (isopentyl) group, a perfluoro (Pentyl) group, perfluoro (neopentyl) group, perfluoro (1-methylpentyl) group, perfluoro (2-methylpentyl) group, perfluoro Perfluorohexyl group, perfluoro (2-ethylhexyl) group, perfluorohexyl group, perfluoro (2-ethylhexyl) Perfluorooctyl group, perfluorononyl group, perfluoro An aliphatic hydrocarbon group containing a fluorine atom such as a fluorodecyl group, a perfluorodecyl group, a perfluorododecyl group and a perfluorooctadecyl group;

Perfluorocyclohexyl group, perfluorocyclohexyl group, perfluorocyclohexyl group, perfluorocyclohexyl group, perfluorocyclohexyl group, perfluorocyclopentyl group, perfluorocyclohexyl group, perfluorocyclohexenyl group, perfluorocycloheptyl group, perfluoro Perfluoro (2-methylcyclohexyl) group, a perfluoro (4-methylcyclohexyl) group, a perfluoro (2-methylcyclohexyl) A perfluoro (2,3-dimethylcyclohexyl) group, a perfluoro (2,3-dimethylcyclohexyl) group, a perfluoro (2,5-dimethylcyclohexyl) group, a perfluoro (2,5-dimethylcyclohexyl) group, a perfluoro (2,5-dimethylcyclohexyl) Perfluoro (3,5-dimethylcyclohexyl) group, a perfluoro (3, 3-dimethylcyclohexyl) group, a perfluoro (4, 4-dimethylcyclohexyl) group, (2,4,6-trimethylcyclohexyl) group, perfluoro (2,2,6,6-tetramethylcyclohexyl) group and perfluoro (3,3,5,5-tetramethylcyclohexyl) An alicyclic hydrocarbon group containing a fluorine atom;

And the like.

Examples of the group in which -CH ₂ - constituting the saturated hydrocarbon group is replaced by -O- and the hydrogen atom contained in the monovalent saturated hydrocarbon group is substituted with a halogen atom include perfluoromethoxy group, perfluoroethoxy group, perfluoropropoxy group, Butoxy group, a perfluoro (isobutoxy) group, a perfluoro (sec-butoxy) group, a perfluoro (isopropoxy) group, a perfluoro (Perfluoroethyl) methoxy group, a (perfluoropropyl) methoxy group, a perfluoroalkoxy group, a perfluorobutyloxy group, a perfluorobutyloxy group, (Perfluoro (isopropenyl)) methoxy group, (perfluoro (isopropenyl)) methoxy group, perfluoro (1-propenyl) (Perfluorobutyl) methoxy group, (perfluorobutyl) methoxy group, (perfluoro (isobutyl)) methoxy group, (perfluoro (Perfluoro (2-butenyl)) methoxy group, perfluoro (1,3-butadienyl) methoxy group, perfluoropentyl methoxy group, perfluoro (isopentyl) (Perfluoro (3-pentyl)) methoxy group, (perfluoro (neopentyl)) methoxy group, (perfluoro Pentyl)) methoxy group, (perfluoro (2-methylpentyl)) methoxy group, (perfluoro (2-pentenyl)) methoxy group, (perfluorohexyl) (Perfluorohexyl) methoxy group, (perfluoro (5-methylhexyl)) methoxy group, (perfluoro (2-ethylhexyl) , (Perfluorodecyl) methoxy group, (perfluorodecyl) methoxy group, (perfluorodecyl) methoxy group, (perfluorododecyl) An alkyloxy group containing a fluorine atom;

Bis (trifluoromethyl) phenylmethyl group; And the like.

As the compound represented by the formula (A-II)

The ring Z ³ and the ring Z ⁴ independently represent a phenyl group which may have a substituent,

R ^a10 and R ^a11 independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,

R ^a12 and R ^a13 independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent,

More preferred are compounds wherein p1 and p2 are 2.

The compound represented by the formula (A-III) is preferably a compound wherein R ^a20 to R ^a23 , R ^a24 and R ^a27 are hydrogen atoms, and R ^a25 and R ^a26 are hydroxyl groups.

X ^{a1 -} is preferably an anion containing at least one element selected from the group consisting of fluorine-containing anions or tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, the fluorine-containing anion represented by formula (6) equation (9) is fluorine-containing anion of a heteropoly acid or isophthalic acid polyester and more preferably containing anionic or tungsten as essential elements represented by, and _{^{CF 3 SO 2 -N - -SO 2}} CF 3, CF 3 SO 3 -, [ PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- or [W ₁₀ O ₃₂ ] ^4- and more preferably CF ₃ SO ^{3 -} , [PW ₁₂ O ₄₀ ] ^3- , and even more preferably [PW ₁₂ O ₄₀ ] ^3- . From the viewpoint of heat resistance, an anion of heteropoly acid or isopoly acid containing tungsten as an essential element can be used.

Examples of the compound represented by the formula (A-1) to (A-228) include a compound represented by the formula (A-I).

Preferably, the compound represented by the formula (A-1) to (A-36), the compound represented by the formula (A-37) to the formula (A- 204), and compounds represented by the formulas (A-205) to (A-228)

More preferably, the compound represented by the formula (A-1) to the formula (A-6), the compound represented by the formula (A-13) -48), compounds represented by formulas (A-181) to (A-198) and compounds represented by formulas (A-211) to (A-216)

More preferably, the compound represented by the formula (A-1) to the formula (A-6), the compound represented by the formula (A-13) -48), < / RTI >

Particularly preferred are the compounds represented by formulas (A-19) to (A-24).

In the above table, X ^{a1 -} , " R ^a (in the following table, * indicates bonding hands) "

In the above table, the ring Z ¹ and the ring Z ² have the following meanings, respectively.

≪ Process for producing compound (A-I) to compound (A-III)

Compound (AI) ~ compound (A-Ⅲ) is compound (AI) ~ (is also referred to as compound (A-Ⅵ)) salts containing the cation portion of the compound (A-Ⅲ) and X ^{a1 -} an alkali metal salt or positive of The assets can be mixed and manufactured.

Examples of the compound (A-VI) include a salt containing a cation moiety of a compound (AI) to a compound (A-III) and a halide ion such as ClO ₄ ^- , OH ^- , PO ₄ ^3- , SO ₄ ^2- , And salts formed from at least one or more anions selected from anions, organic sulfonic acid anions, Lewis acid anions and dye-derived anions.

Examples of halide ions include Cl ^- , Br ^-, and I ^- .

Examples of the organic carboxylic acid anion include benzoic acid ion, alkanoic acid ion, trihaloalkanoic acid ion, and nicotinic acid ion.

Examples of the organic sulfonic acid anion include a benzenesulfonic acid ion, a naphthalenesulfonic acid ion, a p-toluenesulfonic acid ion, and an alkanesulfonic acid ion.

Lewis acid anions include BF ₄ ^- , PF ₆ ^-, and SbF ₆ ^- .

Examples of the dye-derived anion include an anion derived from a phthalocyanine compound and an anion derived from an azo compound, and an anion derived from a phthalocyanine compound is preferable.

Examples of alkali metals forming a salt with X ^{a1 -} include lithium, sodium and potassium.

Compound (A-Ⅵ) X ^a1 with respect ^to-the alkali metal salt or the amount of the proton of the cation and X ^a1 of the compound (A-Ⅵ) ^- is when the charge to balance the added according to the stoichiometric ratio.

Compound (A-Ⅵ) and X ^{a1 -} an alkali metal salt or the proton acid is a mixture of the both may be not dissolved or dissolved in a solvent.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran , Dioxane, water and chloroform.

Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, methanol, ethanol, isopropanol and water are preferable. In the case of such a solution, the solubility of the alkali metal salt of the compound (A-VI) and X ^{a1 -} tends to increase.

When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.

The mixing temperature of the compound (A-VI) with the alkali metal salt or protic acid of X ^{a1 -} is preferably 0 to 150 ° C, more preferably 10 to 120 ° C, and still more preferably 20 to 100 ° C. The mixing time is preferably 1 to 72 hours, more preferably 2 to 24 hours, and further preferably 3 to 18 hours.

When a solvent compatible with water is used, the compound (AI) to the compound (A-III) can be obtained by mixing the above solvent and, if necessary, further stirring for 1 to 3 hours to obtain the precipitate by solid- Can be obtained. If necessary, the resulting compounds (A-I) to (A-III) may be washed with ion-exchanged water or the solvent.

When a solvent which is incompatible with water is used, the compound (AI) to the compound (A-III) can be obtained by mixing the reaction mixture and ion-exchanged water and stirring the mixture for an additional 1 to 3 hours, Can be obtained. If necessary, the solution may be washed with ion-exchanged water or the solvent. Compounds (A-I) to (A-III) can be obtained by removing the solvent from a solution containing the compounds (A-I) to (A-III).

<Coloring Dispersion>

In the present invention, the compound (A-I) is mixed with a solvent to obtain a colored dispersion containing the compound (A-I) and the solvent (E). When the colored curable resin composition is formed by mixing with the resin (B), the polymerizable compound (C), the polymerization initiator (D) or the like after making the colored dispersion, the heat resistance at the time of production by the color filter can be further increased.

Any solvent which can be used as the solvent (E) of the colored curable resin composition can be used as the solvent. The solvent of the colored curable resin composition is preferably an ether ester solvent, more preferably a solvent in which one of the hydroxyl groups of the alkylene glycol or polyalkylene glycol is etherified and the remaining hydroxyl groups are esterified, 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, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether Acetate and the like. They may include singly or plural species.

The amount of the solvent to be used is generally 1 to 50 parts by weight, preferably 2 to 30 parts by weight, and more preferably 3 to 10 parts by weight based on 1 part by weight of the compound (A-I).

In order to prepare the colored dispersion, it is preferable to use a dispersant. As the dispersing agent, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic and the like can be used. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersing agent include trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), propylene (manufactured by Kanko Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by BASF), azerspheres (Manufactured by Techno Corporation), and Disperbyk (manufactured by Big Chemical).

The amount of the dispersant to be used is generally 1 to 1000 parts by weight, preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, and still more preferably 10 to 30 parts by weight, based on 100 parts by weight of the compound (AI) Wealth.

The coloring dispersion may contain a part or all, preferably a part of the resin (B) used in the colored curable resin composition, if necessary. By preliminarily including the resin (B), the dispersibility in the case of producing the colored curable resin composition can be improved. The amount of the resin (B) in the colored dispersion is usually 1 to 300 parts by weight, preferably 10 to 100 parts by weight, more preferably 20 to 70 parts by weight, based on 100 parts by weight of the compound (A-I).

It is preferable to finely disperse the dispersion by appropriately adding the components necessary for production of the dispersion and then using a dispersing device. As the dispersing device, a bead mill device may be used. The beads to be used are generally hard beads such as zirconia beads and have a particle size of 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, and more preferably 0.1 to 0.5 mm.

&Lt; Coloring curable resin composition &

The colored curable resin composition of the present invention includes a composition containing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E) containing the compound (A-I).

The colored curable resin composition of the present invention may suitably contain a polymerization initiator (D1), a leveling agent (F), and the like.

&Lt; Colorant (A) >

The colorant (A) includes the compound (A-I), and the compound (A-1) may include two or more kinds. The colorant (A) may further comprise a dye (A1), a pigment (P).

Dyes (A1) include dyes such as oil soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes and sulfonamide derivatives of acid dyes, of Dyers and Colourists), or known dyes described in the dyeing notes (coloring). Here, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, , Styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted and only the numbers are described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C. I. Solvent Red 45, 49, 125, 130, 218;

C. I. Solvent Blue 4, 5, 37, 67, 70, 90;

C. I. Solvent Dyes such as C. I. Solvent Dyes 1, 4, 5, 7, 34, 35,

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

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91 , 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

CI Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103 , 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234 , 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

C. I. Acid dyes such as C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104,

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

CI Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99 , 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164 , 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210 , 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259 , 260, 268, 274, 275, 293;

C. I. Direct dyes such as C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77,

C. I. Dispulse dyes such as Dispulse Yellow 54, 76,

C. I. Basic Red 1, 10;

C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

C. I. Basic Green 1; C, I. Basic dyes,

C. I. Reactive Yellow 2, 76, 116;

C. I. reactive red 36; Such as C, I. reactive dyes,

C. I. Moderate Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Moderntrad 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84;

C. I. Modern dyes such as C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43,

C. I. I. Bart (vat, tendril) dyes such as I. Bart Green 1,

And the like.

Of these, a yellow dye is preferable.

Two or more of these dyes may be used in combination.

The pigment (P) is not particularly limited, and known pigments can be used, and pigments classified as pigments in the color index (The Society of Dyers and Colourists) are cited.

As the pigment, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137 , 138, 139, 147, 148, 150, 153, 154, 166, 173, 194 and 214;

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, Pigments;

C. I. Pigment Blue 15, 15; 15: 4, 15: 6, and 60;

Green pigments such as C.I. Pigment Green 7, 36, 58;

And the like.

If necessary, the pigment may be subjected to a surface treatment using a rosin treatment, a pigment derivative into which an acidic group or a basic group has been introduced, graft treatment on the surface of the pigment with a polymer compound or the like, atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with water or the like, a removal treatment with an ion exchange method of ionic impurities, or the like. It is preferable that the pigment particle diameters are each uniform.

The pigment may be a pigment dispersion in which the pigment dispersant is uniformly dispersed in the solution by containing a pigment dispersant and dispersing the pigment dispersion. Each of the pigments may be dispersed singly or plural kinds may be mixed and dispersed.

Examples of the pigment dispersing agent include cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and acrylic-based pigment dispersing agents. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersing agent include trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), propylene (manufactured by Kanko Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by BASF), azerspheres (Manufactured by Techno Corporation) and Disperbyk (manufactured by Big Chemical).

The content of the compound (AI) is, for example, at least 0.1 wt%, preferably at least 10 wt%, more preferably at least 30 wt%, and even more preferably at least 50 wt% of the total amount of the colorant (A) , And particularly preferably 70 wt% or more. The upper limit of the content of the compound (A-I) is 100% by weight in the total amount of the colorant (A).

When the dye (A1) is contained, the content of the dye (A1) in the total amount of the colorant (A) is preferably from 0.5 to 90% by weight, more preferably from 40 to 80% to be. When the pigment (P) is contained, the content of the pigment (P) is preferably 1 wt% or more and 99 wt% or less, more preferably 1 wt% or more and 70 wt% or less in the total amount of the colorant (A) More preferably 1% by weight or more and 50% by weight or less.

The content of the colorant (A) is preferably from 0.05% by weight to 70% by weight, more preferably from 0.1% by weight to 60% by weight, and still more preferably from 5% by weight to 50% Or less. When the content of the colorant (A) is within the above range, desired spectral and color intensities can be obtained.

In the present specification, the term &quot; total amount of solid content &quot; refers to the total amount of components excluding the solvent (E) from the colored curable resin composition of the present invention. The total amount of the solid content and the content of each component in the solid content can be measured by a known analytical method such as liquid chromatography or gas chromatography.

&Lt; Resin (B) >

The resin (B) is preferably an alkali-soluble resin. The alkali-soluble resin is a copolymer comprising a structural unit derived from at least one kind of monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

The monomer (a) is preferably prepared by copolymerizing the monomer (b) with at least one of the monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and the ethylenic unsaturated bond and the monomer (c) , And in the case of copolymerization with both the monomer (b) and the monomer (c), a carboxylic acid anhydride may be further reacted.

(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;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2. 2.1] hepto-2-ene and 5,6-dicarboxybicyclo [2. 2. 1] hept-2-ene, and the like;

Unsaturated dicarboxylic acid anhydrides such as maleic anhydride;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as? - (hydroxymethyl) acrylate.

Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable in terms of copolymerization reactivity and solubility of the resin in an aqueous alkali solution.

(b) refers to a polymerizable compound having an ethylenic unsaturated bond with a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) .

(b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" represents at least one member selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as &quot; (meth) acryloyl &quot; and &quot; (meth) acrylate &quot;

(b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b2)") having an oxiranyl group and an ethylenically unsaturated bond (hereinafter also referred to as " ), A monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "(b3)"), and the like. Preferred (b) is a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond.

(b1-1) (hereinafter referred to as "(b1-1)") having a structure in which a linear or branched unsaturated hydrocarbon is epoxidized with the monomer (b1), a monomer (b1-1) having an epoxidized alicyclic unsaturated hydrocarbon (b1-2) (hereinafter referred to as &quot; (b1-2) &quot;). (B1-2) is more preferable because the storage stability of the colored curable resin composition is excellent.

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl- Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5- , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) have.

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl Acrylate (for example, cyclomer A400 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (e.g., A compound represented by the formula (II) and a compound represented by the formula (III).

&Lt; EMI ID =

[In the formulas (II) and (III), R ^a and R ^b independently 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 hydroxyl group.

X ^a and X ^b independently represent a single bond, -R ^c -, -R ^c -O-, -R ^c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Indicates a binding hand with O.]

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, the compounds of the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula -15), more preferably compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15) have.

&Lt; EMI ID =

(42)

Examples of the compound represented by the formula (III) include compounds represented by any one of the formulas (III-1) to (III-15), and among them, the compounds represented by the formulas (III- (III-5), (III-7), (III-9) and (III-11) to (III-15) Include compounds represented by formulas (III-1), (III-7), (III-9) and (III-15).

&Lt; Formula 43 >

&Lt; Formula 44 >

The compound represented by the formula (II) and the compound represented by the formula (III) may be used alone or in combination of the compound represented by the formula (II) and the compound represented by the formula (III). When these compounds are used in combination, the content ratio of the compound represented by formula (II) and the compound represented by formula (III) is preferably 5:95 to 95: 5, more preferably 10:90 to 90: : 10, and more preferably 20:80 to 80:20.

(meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (Meth) acrylate, tricyclo [5. ^2,1 ] ^2,6 ] decan-8-yl (meth) acrylate (also known in the art as "dicyclopentanyl (meth) acrylate""), Tricyclo [5. 2. 1] ^2,6 ] decen-8-yl (meth) acrylate (also known in the art as "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (Meth) acrylates such as acrylate and benzyl (meth) acrylate;

(Meth) acrylate esters having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Diester dicarboxylic acids such as diethyl maleic acid, diethyl fumaric acid and diethyl itaconic acid;

Bicyclo [2. 2.1] hepto-2-ene, 5-methylbicyclo [2. 2.1] hepto-2-ene, 5-ethylbicyclo [2.. 2.1] hepto-2-ene, 5-hydroxybicyclo [2.. 2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.. 2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2. 2.1] hepto-2-ene, 5-methoxybicyclo [2. 2.1] hepto-2-ene, 5-ethoxybicyclo [2.. 2. 1] hepto-2-ene, 5,6-dihydroxybicyclo [2. 2,1] hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2. 2,1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [ 2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.. 2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.. 2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.. 2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [ 2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2. 2.1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.. 2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.. 2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.. 2. 1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [ 2. 1] hepto-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2. 2. 1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl caprylate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl Acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5. 2 ^.1 . O ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [ 2.1] hepto-2-ene is preferable.

Examples of the carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 - tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2. 2.1] hepto-2-ene anhydride and the like. The amount of the carboxylic acid anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [ ^2,1,2,6 ] decyl (meth) acrylate / (meth) acrylic acid copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5 (meth) acrylate / glycidyl . ^2,1 ] ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [ 2. 1. 0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene Resins such as coalescing; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / A resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) Resins such as resins obtained by reacting (meth) acrylic acid with a copolymer; A resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and a resin obtained by further reacting tetrahydrophthalic anhydride.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the unexposed portion has good solubility in the developer, and the resolution of the coloring pattern tends to be improved.

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

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

The content of the resin (B) is preferably 7 to 65% by weight, more preferably 13 to 60% by weight, and still more preferably 17 to 55% by weight, based on the total amount of the solid components. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tends to be improved.

&Lt; Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and / or an acid generated in the polymerization initiator (D), and includes a compound having a polymerizable ethylenically unsaturated bond, and preferably a (meth) acrylic acid ester / RTI &gt;

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned (a), (b) and (c).

Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di Bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (metha) acrylate, tripentaerythritol hexa (Meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (metha) acrylate, propylene glycol-modified pentaerythritol tetra Modified dipentaerythritol hexa (meth) acrylate, Lactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa ) Acrylate.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by weight, more preferably 13 to 60% by weight, and still more preferably 17 to 55% by weight, based on the total amount of the solid components.

The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80 to 80:20, more preferably 35:65 ~ 80:20.

When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the color pattern and the chemical resistance of the color filter tend to be improved.

&Lt; Polymerization initiator (D) >

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical or acid by light and heat action, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, imidazole compounds, triazine compounds and acylphosphine oxide compounds.

The O-acyloxime compound is a compound having a partial structure represented by formula (d1). * Indicates a combined hand.

<Formula 45>

Examples of the O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- -Acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl Benzoyl} -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy- 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-l-imine and N-benzoyloxy- ] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxime compound is preferably selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, -Benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

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

&Lt; EMI ID =

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -2-benzylbutan- ] Butan-1-one. (Commercially available from BASF Co., Ltd.) may be used.

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

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

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373), 2,2'-bis (2- Phenyl) -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 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Examined Patent Publication No. 48-38403, Japanese Unexamined Patent Application Publication No. 62-174204), and 4,4', 5,5 ' (Refer to, for example, JP-A No. 7-10913, etc.) in which the phenyl group at the -position is replaced by a carboalkoxy group. Among them, a compound represented by the following formula and a mixture thereof are preferable.

&Lt; EMI ID =

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4,6-trimethyl- Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

In addition, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl 2-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone and the like; Butyl-2-chloroacridone, benzyl, phenylglyoxylic acid methyl ester, and titanocene compounds.

These are preferably used together with a polymerization initiator (D1) (particularly amines) to be described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and nonimidazole compounds, Is a polymerization initiator comprising an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.05 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total amount of the resin (B) and the polymerizable compound (C).

&Lt; Polymerization Initiator (D1) >

The polymerization initiation aid (D1) is a compound or a sensitizer used for promoting polymerization of a polymerizable compound initiated polymerization by a polymerization initiator. When the polymerization initiator (D1) is included, it is generally used in combination with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoic acid, isoamyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethylbenzoic acid, 2- (Dimethylamino) benzophenone (commonly referred to as micronized ketone), 4,4'-bis (diethylamino) benzophenone, and 4,4'- 4,4'-bis (ethylmethylamino) benzophenone, and the like. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chloro Phenylsulfanyl acetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

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

&Lt; Solvent (E) >

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. As the solvent (E), 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 (-CO- in the molecule (Solvent 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 and a dimethylsulfoxide .

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionic acid, Butyric acid, methyl pyruvic acid, ethyl pyruvic acid, propyl pyruvic acid, methylacetoacetic acid, ethylacetoacetic acid, cyclohexanol acetate and? -Butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene 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, And the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl-3-methoxypropionic acid, ethyl- Ethoxypropionic acid, ethyl-3-ethoxypropionic acid, methyl-2-methoxypropionic acid, ethyl-2-methoxypropionic acid, Ethoxy-2-methylpropionic acid, 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, di Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

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

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

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

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

These solvents may be used alone or in combination of two or more.

Of these, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionic acid, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and N- , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy- Ethoxypropionic acid and N-methylpyrrolidone are more preferable.

The content of the solvent (E) is preferably 70 to 95% by weight, and more preferably 75 to 92% by weight, based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by weight, and more preferably 8 to 25% by weight. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and when the color filter is formed, display quality tends to be improved because the color density is not insufficient.

&Lt; Leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specific examples thereof include Toray Silicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA and Copper Sh8400 (trade names, manufactured by Toray Dow Corning Co.), KP321, KP322, KP323, KP324, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan Cooperation Company).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, there are listed ProRad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co.), Megaface (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, copper R30 (Manufactured by Mitsubishi Materials Electronics Co., Ltd.), Sulfuron (registered trademark) S381, and Sulfuron (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megaface (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.

When the leveling agent (F) is contained, the content thereof is preferably 0.001 wt% or more and 0.2 wt% or less, more preferably 0.002 wt% or more and 0.1 wt% or less in the total amount of the colored curable resin composition, By weight is not less than 0.005% by weight and not more than 0.07% by weight. When the content of the leveling agent is within the above range, the flatness of the color filter can be improved.

&Lt; Other components >

The colored curable 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, if necessary.

&Lt; Process for producing colored curable resin composition >

The colored curable resin composition of the present invention is a colored curable resin composition comprising a compound (AI) and / or a colorant (A) other than the coloring dispersion, the resin (B), the polymerizable compound (C), the polymerization initiator ), A solvent (E), a leveling agent (F), a polymerization initiator (D1) and other components.

When the colorant (A) other than the compound (AI) contains the pigment (P), the pigment (P) is mixed with part or all of the solvent (E) so that the average particle diameter of the pigment It is preferable to disperse by using a bead mill or the like. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended.

After the mixing, it is preferable to filter the colored curable resin composition with a filter having a filter pore size of about 0.01 to 10 mu m.

<Manufacturing Method of Color Filter>

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, the photolithography method is preferable. The photolithography method is a method in which a colored curable resin composition is applied to a substrate, followed by drying to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. The photolithography method can form a colored coating film that is a cured product of the colored composition layer by not using a photomask and / or not developing it during exposure. The thus formed colored pattern or colored coating film is the color filter of the present invention.

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

As the substrate, glass or a resin plate, silicon, and a substrate on which aluminum, silver, silver / copper / palladium alloy thin film and the like are formed is used. A separate color filter layer, a resin layer, a transistor, a circuit, and the like may be formed on these substrates.

The formation of each color pixel by a photolithography method can be performed by a known or common apparatus and conditions. For example, it can be prepared as follows.

First, a colored curable resin composition is coated on a substrate, followed by drying by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.

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

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate the entire surface of the exposure surface with parallel rays or accurately align the photomask with the substrate on which the coloring composition layer is formed.

A colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable.

The developing method may be any of a puddling process, a dipping process, and a spray process. It is also possible to tilt the substrate at an arbitrary angle at the time of development.

It is preferable to rinse after development.

Post-baking is further preferable in addition to the obtained coloring pattern.

The coloring curable resin composition using the compound of the present invention can produce a color filter having particularly excellent heat resistance. The color filter is useful as a color filter used in display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image pickup devices.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, it should be understood that the present invention is not limited to the following Examples, but may be appropriately modified within the scope of the present invention. , All of which are included in the technical scope of the present invention. Unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight".

The compound was identified by mass analysis (LC: Agilent 1200 type, MASS: Agilent LC / MSD type) or elemental analysis (VARIO-EL (Elementar)).

&Lt; Example 1 >

11.0 parts of 2,3,3-trimethylindolenine (manufactured by TOKYO CHEMICAL CO., LTD.) And 19.4 parts of 4-fluorobenzyl bromide were added to 100 parts of toluene, and the mixture was heated under reflux for 14 hours. The precipitate formed after cooling was collected by filtration, washed with 50 parts of chloroform and dried at 60 DEG C for 24 hours to obtain 17.7 parts of a compound represented by the following formula (d-1).

(48)

Identification of the compound represented by the formula (d-1)

(Mass analysis) Ionization mode = ESI +: m / z = 268.1 [M-Br] ⁺

Exact Mass: 347.1

Next, 6.0 parts of the compound represented by the formula (d-1), 0.95 part of squalic acid, 63 parts of 1-butanol and 7.0 parts of pyridine were mixed and heated with stirring at 115 DEG C for 16 hours. The precipitate formed after cooling was collected by filtration and dried at 60 DEG C for 24 hours to obtain 2.3 parts of a compound represented by the formula (SQ-1).

(49)

Identification of the compound represented by the formula (SQ-1)

(Mass spectrometry) Ionization mode = ESI +: m / z = 611.3 [MH] ⁺

Exact Mass: 612.3

&Lt; Example 2 >

2.0 parts of the compound represented by the formula (SQ-1) and 2.0 parts of methyl trifluoromethane sulfonate were placed in 14 parts of methylene chloride, and the mixture was stirred at 20 to 30 ° C for 3 hours. Then, 50 parts of a 5% aqueous solution of sodium hydrogencarbonate was added thereto, and the mixture was partitioned with chloroform. The chloroform was distilled from the organic layer, and the remaining residue was dried at 60 ° C for 24 hours to obtain 2.5 parts of a compound represented by the formula (SQ-1K).

(50)

Identification of the compound represented by the formula (SQ-1K)

(Mass analysis) Ionization mode = ESI +: m / z = 627.3 [M-CF3SO3] ⁺

Exact Mass: 776.3

&Lt; Example 3 >

To 7.7 parts of the compound represented by the formula (SQ-1K), 400 parts of methanol was added and the mixture was stirred at 20 ° C to 30 ° C for 1 hour to obtain a solution. 400 parts of ion-exchanged water was added to this solution and stirred for 2 hours to obtain a solution (SQ-1KA). On the other hand, 28.8 parts of ion-exchanged water was added to 9.6 parts of Phosphor 12 tungstate trihydrogen and stirred at 20 ° C to 30 ° C for 1 hour, followed by addition of 28.8 parts of methanol and stirring for 2 hours to obtain a solution (SQ-1KB). The solution (SQ-1KB) was added to the solution (SQ-1KA) and stirred at 20 ° C to 30 ° C for 12 hours. The resulting precipitate was collected by filtration, washed twice with 200 parts of ion-exchanged water, and then washed twice with 200 parts of methanol. The obtained crystals were dried at 60 DEG C for 24 hours to obtain 11.5 parts of a compound represented by the formula (SQ-1P).

<Formula 51>

&Lt; Synthesis of resin &

A flask equipped with a reflux condenser, a dropping funnel and a stirrer was charged with an appropriate amount of nitrogen, and the flask was purged with nitrogen, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 DEG C with stirring. Then, 19 parts of methacrylic acid, 3 parts of 3,4-epoxytricyclo [5. ^2,1 . O ^2,6 ] decan-8-yl acrylate and 3,4-epoxy tricyclo [5. ^1,1,2,6 ] decane-9-yl acrylate (content ratio: 50:50 in molar ratio) (trade name "E-DCPA", Daicel Co., Ltd.) was added to propylene glycol monomethyl ether acetate 40 Was added dropwise over about 5 hours using a dropping pump. On the other hand, a solution prepared by dissolving 26 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was dropped into a flask over about 5 hours using a separate dropping pump . After completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of the copolymer (43.5%) and the resin (B-1). The obtained resin (B-1) had a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g.

(52)

The polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.

Device ; HLC-8120GPC (manufactured by TOSOH CORPORATION)

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Solid concentration of the test solution; 0.001 to 0.01% by mass

Dose; 50 μL

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500 and A-500 (manufactured by Tosoh Corporation)

The ratio (Mw / Mn) of the polystyrene reduced weight average molecular weight to the number average molecular weight obtained above was used as the molecular weight distribution.

&Lt; Preparation of colored curable resin composition >

<Example 4>

Colorant (A1): 0.3 part of a compound represented by the formula (SQ-1K);

Alkali-soluble resin (B): 50 parts of resin (B-1) (in terms of solid content);

Polymerizable compound (C): 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Yakuza);

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Ilgacure (registered trademark) OXE-01; ) 10 parts;

Solvent (E): 700 parts of propylene glycol monomethyl ether acetate; And

Leveling agent (F): 0.1 part of Megaface (registered trademark) F554 (manufactured by DIC Corporation);

Were mixed to obtain a colored curable resin composition.

&Lt; Example 5 >

Colorant (A1): 0.2 part of a compound represented by the formula (SQ-1P);

Alkali-soluble resin (B): 50 parts of resin (B-1) (in terms of solid content);

Polymerizable compound (C): 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Yakuza);

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Ilgacure (registered trademark) OXE-01; ) 10 parts;

Solvent (E): 400 parts of N-methylpyrrolidone;

Solvent (E): 260 parts of propylene glycol monomethyl ether acetate; And

Leveling agent (F): 0.1 part of Megaface (registered trademark) F554 (manufactured by DIC Corporation);

Were mixed to obtain a colored curable resin composition.

&Lt; Formation of pattern &

A colored curable resin composition was coated on a 2 inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. The reaction mixture was allowed to cool and then the composition layer is formed of a glass substrate and a quartz glass picture the distance from the mask to 100μm, and the exposure device (TME-150RSK; Topcon Corporation (Ltd.)) by using the exposure amount of 150mJ / cm ² under air atmosphere (365nm reference) . A photomask having a 100 μm line and space pattern was used. After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 80 seconds, washed with water and post baked in an oven at 220 DEG C for 20 minutes to form a pattern.

&Lt; Evaluation of heat resistance &

The coating film of the colored curable resin composition was heated at 210 캜 for 20 minutes, and the color difference (? Eab *) before and after the heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The coating films obtained in Examples 4 and 5 were subjected to the above heat resistance evaluation, and as a result, the color difference (? Eab *) was 14.5 and 7.8, respectively, and the compounds of the present invention were found to have excellent heat resistance.

By using the colored curable resin composition containing the compound of the present invention, it is possible to provide a color filter having good heat resistance. The color filter is useful as a color filter used in display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image pickup devices.

Claims (9)

A compound represented by the formula (AI):
&Lt; Formula 1 >

In the formula (A-1)
The ring Z ¹ and the ring Z ² independently represent a heterocyclic group which may have a substituent or an aromatic ring which may have a substituent and at least ^{one of the} rings Z ¹ and Z ² has an onium nitrogen atom,
R ^a1 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, provided that adjacent -CH ₂ - can not be simultaneously substituted with a same group, and -CH ₂ - at the end may be substituted No,
R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms,
X ^{a1 -} represents an anion containing at least one element selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions and tungsten, molybdenum, silicon and phosphorus as essential elements,
a1 represents an integer of 1 to 20,
n is defined to be equal to the positive charge caused by at least one of the onium nitrogen atoms of ring Z ¹ and ring Z ² . A compound according to claim 1, wherein the compound represented by the formula (AI) is a compound represented by the formula (A-II) or a compound represented by the formula (A-III)
(2)

(3)

In formula (A-II), R ^a1 , X ^{a1 -} and a1 have the same meanings as those described in formula (A-1)
The ring Z ³ and the ring Z ⁴ independently represent an aromatic ring which may have a substituent,
R ^a10 and R ^a11 independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent,
R ^a12 and R ^a13 independently represent a hydrogen atom, a halogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or one R ^a12 and one R ^a13 bond to each other to form a ring having 2 to 6 carbon atoms A divalent aliphatic hydrocarbon group,
p1 and p2 represent an integer of 0 to 2,
In formula (A-III), R ^a1 , X ^{a1 -} and a1 have the same meanings as defined in formula (A-1)
R ^a20 to R ^a23 independently represent a hydrogen atom, a halogen atom, a hydroxy group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and may have a substituent,
R ^a24 to R ^a27 independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a trifluoromethyl group or -NHCO-R ^a32 ,
R ^a28 to R ^a31 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the hydrocarbon group may be ^replaced by -O-, -S-, -N (R ^a33 ) -, -SO ₂ - or -CO-, provided that adjacent -CH ₂ - can not be simultaneously substituted with a same group, and -CH ₂ - at the terminal can not be substituted,
R ^a20 and R ^a24 , R ^a21 and R ^a25 , R ^a22 and R ^a26 , R ^a23 and R ^a27 each may form a ring together with the carbon atoms to which they are bonded,
R ^a20 and R ^a28 , R ^a21 and R ^a29 , R ^a22 and R ^a30 , R ^a23 and R ^a31 may form a ring together with the nitrogen atom and the carbon atom to which they are bonded,
R ^a28 and R ^a29 , R ^a30 and R ^a31 may form a ring with the nitrogen atom to which they are bonded, R ^a32 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the saturated hydrocarbon group -CH ₂ - may be substituted with -O-, -S-, -N (R ^a34 ) -, -SO ₂ - or -CO-, provided that adjacent -CH ₂ - And -CH ₂ - at the terminal may not be substituted,
R ^a33 and R ^a34 are each independently, represent a hydrogen atom, an aralkyl group having from 1 to 20 carbon atoms or a saturated hydrocarbon group having a carbon number of 7-10 with each other. The method of claim 2,
The ring Z ³ and the ring Z ⁴ in the formula (A-II) independently represent a phenyl group which may have a substituent,
R ^a10 and R ^a11 independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent,
R ^a12 and R ^a13 independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent,
and p1 and p2 represent 2. The compound according to claim 1 or 2, wherein X ^{a1 -} is an anion containing at least one element selected from the group consisting of fluorine-containing anions or tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements. The compound according to claim 1 or 2, wherein R ^a1 is an unsubstituted saturated hydrocarbon group having 1 to 20 carbon atoms. A colored dispersion comprising the compound of claim 1 and a solvent (E). A colored curable resin composition comprising a compound according to claim 1, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). A color filter formed from the color-curable resin composition according to claim 7. A display device comprising the color filter according to claim 8.