TWI712654B - Compound and coloring composition - Google Patents

Abstract

The present invention provides a novel coloring composition which is able to use in color filters and the like.

The present invention is related to a coloring composition containing a compound represented by formula (I) and a resin.

Description

Compound and coloring composition

The present invention relates to compounds and coloring compositions.

For yellow pigments, compounds with an isoindoline skeleton such as C.I. Pigment Yellow 139 are known, which have been used in printing inks, coatings and other fields to display colors using reflected or transmitted light.

The main points of the present invention are as follows:

[1] A coloring composition containing a compound represented by formula (I) and a resin.

In the formula (I), L ¹ represents -CO- or -SO ₂ -.

R ¹ to R ⁵ and R ¹² to R ¹³ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ ,- SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) _2. Halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group with 1 to 40 carbon atoms or optionally substituted heterocyclic group.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ each independently represent an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group.

R ¹⁰² represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

M is a hydrogen atom or an alkali metal atom.

When there are plural R ¹⁰¹ , R ¹⁰² and M, these may be the same or different.

The wavy line indicates the E body or the Z body.

[2] The colored composition according to the item [1], wherein the compound represented by formula (I) is a compound represented by formula (I-a).

In the formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

L ² represents -CO- or -SO ₂ -.

R ¹⁴ represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group.

[3] The colored composition as described in [2], wherein R ¹¹ and R ¹⁴ are the same group, and L ¹ and L ² are the same group.

[4] The coloring composition as described in [2] or [3], wherein R ¹¹ and R ¹⁴ are each independently an optionally substituted alkyl group having 1 to 40 carbon atoms, or optionally substituted benzene A group, a naphthyl group which may have a substituent, a tetrahydronaphthyl group which may have a substituent, a thienyl group which may have a substituent, a furyl group which may have a substituent, or a pyridyl group which may have a substituent.

[5] The colored composition according to the item [1], wherein the compound represented by formula (I) is a compound represented by formula (I-b).

In the formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

R ²⁰ and R ³⁰ are bonded to form ring Q.

The ring Q may have a substituent, and the number of members of the ring may be from 5 to 7. The ring Q may be a hydrocarbon ring or a heterocyclic ring. In the ring Q, a monocyclic ring of 5 to 7 members selected from a hydrocarbon ring and a heterocyclic ring or a condensed ring formed by the condensation of the monocyclic ring may be bonded.

[6] The colored composition according to the item [5], wherein the compound represented by formula (I) is a compound represented by formula (I-c).

In the formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

R ⁶ and R ⁷ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, Cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

R ¹⁰¹ , R ¹⁰² and M have the same meaning as above.

[7] The colored composition according to any one of [1] to [6], wherein R ¹ is a hydrogen atom, and R ² to R ⁵ are each independently a hydrogen atom or a nitro group.

[8] A colored curable resin composition comprising the colored composition described in any one of [1] to [7], a polymerizable compound, and a polymerization initiator.

[9] A color filter which is formed of the coloring curable resin composition described in [8].

[10] A liquid crystal display comprising the color filter described in [9].

[11] A compound represented by formula (II).

In the formula (II), R ¹ to R ⁵ and R ¹² to R ¹³ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group with 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ each independently represent an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group.

R ¹⁰² represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

M is a hydrogen atom or an alkali metal atom.

When there are plural R ¹⁰¹ , R ¹⁰² and M, these may be the same or different.

The wavy line indicates the E body or the Z body.

[12] A compound represented by formula (II-a1).

In the formula, R ¹ to R ⁵ and R ¹² to R ¹³ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON (R ¹⁰² ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

R ¹⁰¹ represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group.

R ¹⁰² represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹¹ represents a heterocyclic group which may have a substituent or a hydrocarbon group of 1 to 40 carbons which may have a substituent. However, when R ¹¹¹ is a substituted hydrocarbon group with 1 to 40 carbons, any one of R ¹² and R ¹³ is -SO ₂ -R ¹¹¹ , and the other of R ¹² and R ¹³ is a cyano group, R At least one of ² to R ⁵ means -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ ,- CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro Group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

M is a hydrogen atom or an alkali metal atom.

When there are plural R ¹⁰¹ , R ¹⁰² and M, these may be the same or different.

The wavy line indicates the E body or the Z body.

[13] The compound according to the item [12], wherein R ¹¹¹ is a heterocyclic ring which may have a substituent.

[14] A compound represented by formula (I-b).

[式(I-b)中，L¹，係表示-CO-或-SO₂-。

[In formula (Ib), L ¹ represents -CO- or -SO ₂ -.

R ²⁰ and R ³⁰ are bonded to form ring Q.

The ring Q may have a substituent, and the number of members of the ring may be from 5 to 7. The ring Q may be a hydrocarbon ring or a heterocyclic ring. In the ring Q, a monocyclic ring of 5 to 7 members selected from a hydrocarbon ring and a heterocyclic ring may be bonded, or the monocyclic ring is a condensed ring formed by condensation.

R ¹ to R ⁵ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, Cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

R ² and R ³ , R ³ and R ^4, and R ⁴ and R ⁵ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ each independently represent an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group.

R ¹⁰² represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

M is a hydrogen atom or an alkali metal atom.

When there are plural R ¹⁰¹ , R ¹⁰² and M, these may be the same or different.

The wavy line indicates the E body or the Z body. ]

The coloring composition of the present invention contains a compound represented by formula (I) (hereinafter, also referred to as compound (I)) and a resin (hereinafter, also This is called the case of resin (B)).

Compound (I) also includes its tautomers or their salts.

Compound (I) can be used as a colorant.

The coloring composition of the present invention may contain one kind or two or more kinds of compound (I).

The coloring composition of the present invention also contains a coloring agent other than the compound (I) (hereinafter, also referred to as coloring agent (A1). In the following, compound (I) and coloring agent (A1) are also collectively referred to as "coloring agent" (A)”).

The coloring agent (A1) may contain one or more coloring agents.

The colorant (A1) preferably contains a yellow colorant or a green colorant.

The coloring composition of the present invention preferably contains a solvent (E). Meanwhile, when the coloring composition of the present invention contains the solvent (E), it is preferable that the compound (I) is dispersed in the solvent (E).

Furthermore, the colored curable resin composition of the present invention contains a polymerizable compound (C) and a polymerization initiator (D) in addition to the compound and resin represented by formula (I).

The colored curable resin composition of the present invention may contain a polymerization initiation assistant (D1).

The colored composition and colored curable resin composition of the present invention may further contain a leveling agent (F) and an antioxidant.

The coloring composition and coloring curable resin composition of the present invention can be made into a color filter with a lower retardation value than a color filter formed of a coloring curable resin composition containing C.I Pigment Yellow 185.

<Compound (I)>

Compound (I) is a compound represented by formula (I).

In the formula (I), L ¹ represents -CO- or -SO ₂ -.

R ¹ to R ⁵ and R ¹² to R ¹³ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ ,- SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) _{2. A} halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ each independently represent an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group.

R ¹⁰² represents a hydrogen atom, an optionally substituted hydrocarbon group with 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

M is a hydrogen atom or an alkali metal atom.

When there are plural R ¹⁰¹ , R ¹⁰² and M, these may be the same or different.

The wavy line indicates the E body or the Z body.

L ¹ is preferably -CO-.

In compound (I), R ¹ to R ⁵ and R ¹² to R ¹³ are each independently a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , halogen atom, cyano group, nitro group, -SO ₃ M , -CO ₂ M, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

The carbon number of the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² is 1 to 40, preferably 1 to 30, more preferably 1 to 20, and 1 to 15 It is better, and it is even better with 1 to 10.

The hydrocarbon groups of 1 to 40 carbons represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may be aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and the aliphatic hydrocarbon groups may be saturated or unsaturated , It can also be chain or alicyclic.

The saturated or unsaturated chain hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include methyl, ethyl, propyl, butyl, pentyl, hexyl, Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, heptadecyl, octadecyl and eicosyl and other linear alkyl groups; isopropyl, (2 -Methyl)propyl, isobutyl, second butyl, tertiary butyl, (2-ethyl)butyl, isopentyl, neopentyl, tertiary pentyl, (1-methyl)pentyl Group, (2-methyl)pentyl, (1-ethyl)pentyl, (3-ethyl)pentyl, isohexyl, (5-methyl)hexyl, (2-ethyl)hexyl and (3 -Ethyl)heptyl and other branched chain alkyl groups, etc.; vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, (1-methyl)vinyl, 2-butene Alkenyl, 3-butenyl, 1,3-butadienyl, (1-(2-propenyl)) vinyl, (1,2-dimethyl)propenyl and 2-pentenyl Wait. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 8, 1 to 5 are particularly good. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is particularly preferred.

The saturated or unsaturated alicyclic hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclo Pentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1, 3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2, 6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4, 4-Dimethylcyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl and 3,3,5,5-tetramethyl ring Cycloalkyl groups such as hexyl, 4-pentylcyclohexyl, 4-octylcyclohexyl, 4-cyclohexylcyclohexyl, etc.; cyclohexenyl (e.g. cyclohex-2-ene, cyclohex-3-ene), cycloheptyl Cycloalkenyl such as alkenyl and cyclooctenyl; norbornyl, adamantyl, bicyclo[2.2.2]octane, etc. The carbon number of the alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, more preferably 4 to 20, still more preferably 4 to 15, even more preferably 5 to 15, and even more preferably 5 to 5 10 is especially good. Among them, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl are particularly preferred.

The saturated or unsaturated hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ^101, and R ¹⁰² may be a combination of the above-listed hydrocarbon groups, and examples include cyclopropylmethyl, ring Propyl ethyl, cyclobutyl methyl, cyclobutyl ethyl, cyclopentyl methyl, cyclopentyl ethyl, cyclohexyl methyl, cyclohexyl ethyl, etc. Alkyl groups bonded with more than one alicyclic hydrocarbon group The carbon number is preferably from 4 to 30, more preferably from 4 to 20, and even more preferably from 4 to 15.

The aromatic hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include phenyl, o-tolyl, m-tolyl, p-tolyl, 2, 3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3, 5-Dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-tertiary butylphenyl, m- Tertiary butylphenyl, p-tertiary butylphenyl, mesityl, 4-ethylphenyl, 4-butylphenyl, 4-pentylphenyl, 2,6-bis(2- Propyl) phenyl, 4-cyclohexylphenyl, 2,4,6-trimethylphenyl, 4-octylphenyl, 4-vinylphenyl, 1-naphthyl, 2-naphthyl, 5 ,6,7,8-Tetrahydro-1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, fluorenyl, phenanthrenyl and anthrenyl, pyrenyl, etc.

The carbon number of the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and even more preferably from 6 to 15.

The aromatic hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may be a combination of the above-listed hydrocarbon groups, including benzyl, phenethyl, 1-methyl Arylalkyls such as phenyl-1-phenylethyl; arylalkenyls such as phenylethenyl (phenylvinyl); arylalkenyls such as phenylvinyl; biphenyl, triple Phenyl and other phenyl groups bonded with more than one phenyl group; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl)methyl)phenyl, etc., whose carbon number is from 4 to 30 is preferable, 4-20 is more preferable, and 4-15 is even more preferable.

The hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have a substituent. The substituent may be monovalent or divalent. For the divalent substituent, it is preferable that two bonding sites are bonded to the same carbon atom to form a double bond.

The monovalent substituents include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, tertiary butoxy, pentoxy Oxy, hexyloxy, (2-ethyl)hexyloxy, heptyloxy, octyloxy, nonyloxy, phenoxy and o-tolyloxy and other hydrocarbon groups with carbon numbers 1 to 10 are bonded in a single Pendant oxy; methylsulfanyl, ethylsulfanyl, propylsulfanyl, butylsulfanyl and other C1-C10 alkylsulfanyl groups (alkylsulfanyl); methylsulfanyl; acetylsulfanyl, propylsulfanyl , Butanyl, 2,2-dimethylpropanyl, pentanyl, hexyl, (2-ethyl) hexyl, heptyl, octyl, nonyl and benzyl and other bonds The carbonyl group of a hydrocarbon group having 1 to 12 carbons; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tertiary butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, (2 -Ethyl) hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, phenoxycarbonyl, o-tolyloxycarbonyl and other oxycarbonyl groups bonded to hydrocarbon groups with 1 to 10 carbon atoms; Amino; N-methylamino, N,N-dimethylamino, N-ethylamino, N,N-diethylamino, N-propylamino, N,N-dipropylene Amine group, N-isopropylamino group, N,N-diisopropylamino group, N-butylamino group, N,N-dibutylamino group, N-isobutylamino group, N, N-diisobutylamino, N-second butylamino, N,N-disecond butylamino, N-tertiary butylamino, N,N-di-tertiary butylamino , N-pentylamino, N,N-dipentylamino, N-(1-ethylpropyl)amino, N,N-bis(1-ethylpropyl)amino, N-hexyl Amino, N,N-dihexylamino, N-(2-ethyl)hexylamino, N,N-bis(2-ethyl)hexylamino, N-heptylamino, N,N- Diheptylamino, N-octylamino, N,N-dioctylamino, N-nonylamino, N,N-dinonylamino, N-phenylamino, N,N -Diphenylamino, N,N-ethylmethylamino, N,N-propylmethylamino, N,N-isopropylmethylamino, N,N-butylmethylamino, N,N-tertiary butylmethylamino and N,N-phenylmethylamino and other amino groups substituted with 1 or 2 hydroxyl groups with 1 to 10 carbon atoms; sulfamsulfonyl; N-methylamine Sulfonyl, N,N-dimethylsulfasulfonyl, N-ethylsulfasulfonyl, N,N-diethylsulfasulfonyl, N-propylsulfasulfonyl, N,N- Dipropyl sulfasulfonyl, N-isopropyl sulfasulfonyl, N,N-diisopropyl sulfasulfonyl, N-butyl sulfasulfonyl, N,N-dibutyl sulfasulfon Group, N-isobutyl sulfasulfonyl, N,N-diisobutyl sulfasulfonyl, N-second butyl sulfasulfonyl, N,N-di-second butylsulfasulfonyl, N-Third-Butylsulfasulfonyl, N,N-Di-tertiary-Butylsulfasulfonyl, N-pentylsulfasulfonyl, N,N-Dipentylsulfasulfonyl, N-(1 -Ethylpropyl)sulfasulfonyl, N,N-bis(1-ethylpropyl)sulfasulfonyl, N-hexylsulfasulfonyl, N,N-dihexylamine Sulfonyl, N-(2-ethyl)hexylsulfasulfonyl, N,N-bis(2-ethyl)hexylsulfasulfonyl, N-heptylsulfasulfonyl, N,N-diheptyl Sulfonyl, N-octylsulfasulfonyl, N,N-dioctylsulfasulfonyl, N,N-octylmethylsulfasulfonyl, N-nonylsulfasulfonyl, N,N-Dinonylsulfasulfonyl, N-phenylsulfasulfonyl, N,N-diphenylsulfasulfonyl, N,N-ethylmethylsulfasulfonyl, N,N -Propyl methylsulfamate, N,N-isopropyl methylsulfamate, N,N-butyl methylsulfamate, N,N-tertiary butyl methylsulfamate and N, N-Phenylmethylsulfamate, etc., substituted by 1 or 2 hydrocarbon groups with 1 to 10 carbon atoms; Formamido; Acetamido, propionamido, butyamido , 2,2-Dimethyl acetamido, pentamido, hexamido, (2-ethyl) hexamido, heptamido, octamido, nonamido, decanoate Amido groups, undecamidoamino groups, dodecamidoamino groups, benzamidoamino groups, and other amino groups substituted with carbonyl groups bonded to hydrocarbon groups with 1 to 12 carbon atoms; hydroxyl; fluorine Halogen atoms such as atom, chlorine atom, bromine atom and iodine atom; carboxyl group; sulfonic acid group; nitro group; cyano group; -SO ₃ M; -CO ₂ M; formoxy group; acetoxy group, propoxy group , Butanyloxy, 2,2-dimethylpropanyloxy, pentyloxy, hexyloxy, (2-ethyl) hexyloxy, heptyloxy, octyloxy, nonyl A carbonyloxy group and a benzyloxy group bonded to a hydrocarbon group with 1 to 10 carbons; methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentyl Sulfonyl, hexylsulfonyl, (2-ethyl)hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, phenylsulfonyl And p-tolylsulfonyl and other sulfonyl groups substituted with a hydrocarbon group having 1 to 10 carbons; aminomethyl; N-methylaminomethyl, N,N-dimethylaminomethyl Group, N-ethylaminomethanyl, N,N-diethylaminomethanyl, N-propylaminomethanyl, N,N-dipropylaminomethanyl, N- Isopropylaminoformyl, N,N-diisopropylaminoformyl, N-butylaminoformyl, N,N-dibutylaminoformyl, N-isobutyl N,N-diisobutylaminomethanyl, N,N-diisobutylaminomethanyl, N-second butylaminomethanyl, N,N-di-secondbutylaminomethanyl, N- Tertiary butylaminomethanyl, N-tertiary butylaminomethanyl, N,N-di-tertiarybutylaminomethanyl, N-pentylaminomethanyl, N,N -Dipentylaminomethanyl, N-(1-ethylpropyl)aminomethanyl, N,N-bis(1-ethylpropyl)aminomethanyl, N-hexylamino Formyl, N,N-dihexylaminomethanyl, N-(2-ethyl)hexylaminomethanyl, N,N-bis(2-ethyl)hexylaminomethanyl, N -Heptylaminoformyl, N,N-diheptylaminoformyl, N-octylaminoformyl, N,N-dioctylaminoformyl, N-nonylamine Base formaldehyde, N, N -Dinonylaminomethanyl, N-phenylaminomethanyl, N,N-diphenylaminomethanyl, N,N-ethylmethylaminomethanyl, N,N -Propylmethylaminomethanyl, N,N-isopropylmethylaminomethanyl, N,N-butylmethylaminomethanyl, N,N-tertiary butylmethylaminomethanyl And N,N-phenylmethylaminomethanyl and other aminomethanyl groups substituted with 1 or 2 hydrocarbon groups with 1 to 10 carbons; trifluoromethyl, perfluoroethyl, perfluoropropyl Base, Perfluoroisopropyl, Perfluorobutyl, Perfluoropentyl, Perfluorohexyl, Perfluoroheptyl, Perfluorooctyl, Perfluorononyl, Perfluorodecyl, Perfluorocyclohexyl, Perfluorobenzene Perfluoroethylmethyl, Perfluoropropylmethyl, Perfluoroisopropylmethyl, Perfluorobutylmethyl, Perfluoropentylmethyl, Perfluorohexylmethyl, Perfluoroheptylmethyl, All Fluorooctylmethyl, perfluorononylmethyl; 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4,6-trifluorophenyl and other fluorine-substituted carbon numbers 1 to 10 hydrocarbon group; -CO-SH, -CO-S-CH ₃ , -CO-S-CH ₂ CH ₃ , -CO-S-CH ₂ -CH ₂ -CH ₃ , -CO-S-CH ₂ -CH ₂ -CH ₂ -CH _3, etc. and the carbonyl group that has been bonded to the sulfur atom of an alkyl group having 2 to 10 carbons, -CO-SC ₆ H _5, etc., and the aryl group having 7 to 20 carbons The sulfur atom is bonded to the carbonyl group, etc.

The divalent substituents include pendant oxy groups, thioketone groups, imino groups, imino groups substituted with alkyl groups having 1 to 20 carbons (preferably 1 to 10 carbons), and 6 to 20 aryl substituted imino groups, etc. For the imino group substituted with alkyl, CH ₃ -N=, CH ₃ -CH ₂ -N=, CH ₃ -(CH ₂ ) ₂ -N=, CH ₃ -(CH ₂ ) ₃ -N = Wait. The imino group substituted with an aryl group includes C ₆ H ₅ -N= and the like.

As for the substituent of the hydrocarbon group having 1 to 40 carbons, preferably a hydrocarbon group having 1 to 10 carbons is bonded to an oxy group on one side; a carbonyl group having a hydrocarbon group having 1 to 12 carbons is bonded; The oxycarbonyl group of a hydrocarbon group of 1 to 10; an amine group; an amine group substituted by one or two hydrocarbon groups of 1 to 10 carbon atoms; an sulfonamide group substituted by one or two hydrocarbon groups of 1 to 10 carbon atoms ; Amino group that replaces the carbonyl group of a hydrocarbon group with 1 to 12 carbon atoms; hydroxyl group; fluorine atom, chlorine atom, bromine atom; carboxyl group; sulfonic acid group; nitro group; cyano group; bonded with carbon number 1 to 10 The carbonyloxy group of the hydrocarbyl group; the sulfonyl group bonded to the hydrocarbyl group having 1 to 10 carbons; the aminomethanyl group; the aminomethanyl group substituted with one or two hydrocarbyl groups having 1 to 10 carbons; Fluorine-substituted hydrocarbon groups with carbon numbers of 1 to 10; pendant oxy groups; -SO ₃ M; -CO ₂ M.

The heterocyclic group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may be monocyclic or polycyclic, and preferably contains a heteroatom as a constituent element of the ring The heterocycle. The hetero atom includes a nitrogen atom, an oxygen atom, and a sulfur atom.

The heterocyclic ring represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ^101, and R ¹⁰² specifically includes a ring represented by the following formula. The carbon number of the heterocyclic group is preferably 3 to 30, more preferably 3 to 22, more preferably 3 to 20, more preferably 3 to 18, even more preferably 3 to 15, and even more preferably 3 to 14. Especially good.

等單環系飽和雜環；2,5-二甲基吡咯等吡咯、2-甲基吡唑、3-甲基吡唑等吡唑、咪唑、1,2,3-三唑、1,2,4-三唑等5員環系不飽和雜環；吡啶、嗒

、6-甲基嘧啶等嘧啶、吡

、1,3,5-三

等6員環系不飽和雜環；吲唑、吲哚啉、異吲哚啉、吲哚、吲哚

、苯并咪唑、喹啉、異喹啉、5,6,7,8-四氫(3-甲基)喹

啉、3-甲基喹

啉等喹

啉、喹唑啉、

啉、呔

、萘啶、嘌呤、喋啶、苯并吡唑、苯并哌啶等縮合二環系雜環；咔唑、吖啶、啡

等縮合三環系雜環等。 For heterocycles containing nitrogen atoms, aziridine, azetidine, pyrrolidine, piperidine, piperidine

Monocyclic saturated heterocycles; 2,5-dimethylpyrrole and other pyrroles, 2-methylpyrazole, 3-methylpyrazole and other pyrazoles, imidazole, 1,2,3-triazole, 1,2 ,4-Triazole and other 5-membered ring system unsaturated heterocycles; pyridine, tetra

, 6-methylpyrimidine and other pyrimidines, pyrimidines

, 1,3,5-three

6-membered ring system unsaturated heterocyclic ring; indazole, indoline, isoindoline, indole, indole

, Benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro(3-methyl)quine

Morinoline, 3-methylquine

Quinoline

Quinazoline,

Morpholino

, Naphthyridine, purine, pteridine, benzopyrazole, benzopiperidine and other condensed bicyclic heterocycles; carbazole, acridine, phenanthrene

Such as condensed tricyclic heterocycles and so on.

烷、1,4-二

烷、1-環戊基二氧戊烷(cyclopentyl dioxolane)等單環系飽和雜環；1,4-二氧雜螺[4.5]癸烷、1,4-二氧雜螺[4.5]壬烷等二環系飽和雜環；α-乙內酯、β-丙內酯、γ-丁內酯、γ-戊內酯及δ-戊內酯等內酯系雜環；2,3-二甲基呋喃、2,5-二甲基呋喃等5員環系不飽和雜環；2H-哌喃、4H-哌喃等6員環系不飽和雜環；1-苯并呋喃、4-甲基苯并哌喃等苯并哌喃、苯并二

呃、二氫苯并哌喃(chroman)、異二氫苯并哌喃等縮合二環系雜環；二苯并哌喃、二苯并呋喃等縮合三環系雜環等。 For heterocycles containing oxygen atoms, ethylene oxide, butylene oxide, tetrahydrofuran, tetrahydropyran, 1,3-di

Alkane, 1,4-bis

Monocyclic saturated heterocycles such as alkane and 1-cyclopentyl dioxolane (cyclopentyl dioxolane); 1,4-dioxaspiro[4.5]decane, 1,4-dioxaspiro[4.5]nonane Bicyclic saturated heterocycles; α-hydantoin, β-propiolactone, γ-butyrolactone, γ-valerolactone and δ-valerolactone and other lactone heterocycles; 2,3-dimethyl 5-membered ring system unsaturated heterocyclic ring such as methyl furan and 2,5-dimethylfuran; 6-membered ring system unsaturated heterocyclic ring such as 2H-pyran and 4H-pyran; 1-benzofuran, 4-methyl Benzopiperan and benzobis

Er, condensed bicyclic heterocycles such as dihydrobenzopiperan (chroman) and isodihydrobenzopyran; condensed tricyclic heterocycles such as dibenzopyran and dibenzofuran, etc.

As for the heterocyclic ring containing a sulfur atom, a 5-membered ring system saturated heterocyclic ring such as dithiolane; sulfurized cyclopentane (thiane), 1,3-disulfide cyclopentane, 2-methyl 1,3- 6-membered ring system saturated heterocyclic ring such as cyclopentane disulfide; 5-membered ring such as thiophene such as 3-methylthiophene, 2-carboxythiophene, 4H-thiopyran, benzothiopyran, etc. System unsaturated heterocyclic ring; benzothiophene and other condensed bicyclic heterocyclic ring; thianthene, dibenzothiophene and other condensed tricyclic heterocyclic ring, etc.

唑等

唑、2-甲基異

唑、3-甲基異

唑等異

唑等單環系不飽和雜環；苯并

唑、苯并異

唑、苯并

、苯并二

烷、苯并咪唑啉等縮合二環系雜環；啡

等縮合三環系雜環等。 For heterocyclic rings containing nitrogen and oxygen atoms, morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, 2-methyl-2-piperidone can be mentioned Monocyclic saturated heterocyclic ring; 4-methyl

Azole

Azole, 2-methyl iso

Azole, 3-methyl iso

Azoles

Monocyclic unsaturated heterocycles such as azoles; benzo

Azole, benziso

Azole, benzo

Benzodi

Alkyl, benzimidazoline and other condensed bicyclic heterocycles;

Such as condensed tricyclic heterocycles and so on.

等縮合三環系雜環等。 Examples of heterocyclic rings containing nitrogen and sulfur atoms include monocyclic heterocycles such as thiazoles such as 3-methylthiazole and 2,4-dimethylthiazole; condensed bicyclic heterocycles such as benzothiazole; and phenothiazoles.

Such as condensed tricyclic heterocycles and so on.

The heterocyclic ring may be a combination of the above-listed hydrocarbon groups, such as tetrahydrofuryl methyl and the like.

Other heterocycles may be represented by the following groups.

The aforementioned heterocyclic group may be a heterocyclic group formed by bonding with two or more of R ¹ to R ⁵ . Such a heterocyclic group has a benzene ring bonded to R ¹ to R ⁵ and has a ring structure of 2 or more rings. Examples of the ring structure having two or more rings include the structure of the following formula.

In addition, the bonding position of the above heterocyclic ring is a structure in which any hydrogen atom contained in each ring is removed.

The heterocyclic group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have a substituent. Examples of the substituent include the same substituents that the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have. Furthermore, when the aforementioned heterocyclic ring contains a nitrogen atom as its constituent element, the above-mentioned hydrocarbon group may be bonded as a substituent to the nitrogen atom.

The following describes -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -of R ¹ to R ⁵ , R ⁶ , R ⁷ , R ¹¹ , R ¹² , R ¹³ R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCON(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON( R ¹⁰² ) ₂ , halogen atom, -SO ₃ M, -CO ₂ M.

-CO-R ¹⁰² includes formyl, acetyl, propyl, butyryl, 2,2-dimethyl propyl, pentam, hexyl, (2-ethyl) hexyl Carbonyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, icosanoyl, benzyl and other carbonyl groups bonded to hydrocarbon groups with carbon numbers 1 to 41 Etc., and preferably a carbonyl group to which a hydrocarbon group having 1 to 12 carbons is bonded.

-COO-R ¹⁰¹ includes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tertiary butoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, hexoxycarbonyl, (2-ethyl)hexoxycarbonyl, Heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, and icosanoyloxycarbonyl groups bonded to hydrocarbon groups with 1 to 40 carbon atoms, and An oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms is bonded is preferred.

-OCO-R ¹⁰² includes formoxy, acetoxy, propoxy, butoxy, 2,2-dimethylpropoxy, pentoxy, and hexoxy Group, (2-ethyl) hexyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, dodecanoyloxy A carbonyloxy group and a benzyloxy group bonded to a hydrocarbon group having 1 to 41 carbon atoms, etc., and preferably a carbonyloxy group bonded to a hydrocarbon group having 1 to 12 carbon atoms.

-OR ¹⁰² includes hydroxyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, tertiary butoxy, pentoxy Base, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, (2-ethyl)hexyloxy, eicosyloxy, 1-benzene Ethoxy, 1-methyl-1-phenylethoxy, phenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy Phenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,2-dicyanophenoxy, 2 ,3-dicyanophenoxy, 2,4-dicyanophenoxy, 2,5-dicyanophenoxy, 2,6-dicyanophenoxy, 3,4-dicyano Phenoxy, 3,5-dicyanophenoxy, 4-methoxyphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-ethoxyphenoxy , 2-ethoxyphenoxy, 3-ethoxyphenoxy, etc. bonded to a hydrocarbon group with carbon number of 1 to 40, etc., and bonded to a hydrocarbon group with carbon number of 1 to 10, etc. Better.

-SO ₂ -R ¹⁰¹ includes methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2-ethylsulfonyl Base) hexyl sulfonyl, heptyl sulfonyl, octyl sulfonyl, nonyl sulfonyl, decyl sulfonyl, undecyl sulfonyl, dodecyl sulfonyl, icosyl sulfonyl Sulfonyl group, phenylsulfonyl group, p-tolylsulfonyl group and the like bonded to a hydrocarbon group with carbon number 1 to 40, etc., and sulfonyl group bonded to a hydrocarbon group with carbon number 1 to 10, etc. good.

-SO ₂ N(R ¹⁰² ) _{2 can} include sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, N-isopropyl N-butyl sulfasulfonyl, N-butyl sulfasulfonyl, N-isobutyl sulfasulfonyl, N-second butyl sulfasulfonyl, N-tertiary butyl sulfasulfonyl, N-pentyl Sulfonamide, N-(1-ethylpropyl) Sulfonyl, N-hexyl Sulfonyl, N-(2-ethyl)hexyl Sulfonyl, N-heptyl Sulfonyl Group, N-octylsulfasulfonyl, N-nonylsulfasulfonyl, N-decylsulfasulfonyl, N-undecylsulfasulfonyl, N-dodecylsulfasulfonyl, N -Eicosyl sulfasulfonyl and N-phenylsulfasulfonyl and other sulfasulfonyl groups substituted with a hydrocarbon group of 1 to 40 carbons; N,N-dimethylsulfasulfonyl, N, N-Ethyl Methylsulfasulfonyl, N,N-Diethylsulfasulfonyl, N,N-Propyl Methylsulfasulfonyl, N,N-Dipropylsulfasulfonyl, N, N-isopropyl methylsulfamate, N,N-diisopropylsulfamethine, N,N-tertiary butyl methylsulfamate, N,N-diisobutylsulfamate , N,N-di-second butylsulfamate, N,N-di-tertiary butylsulfamate, N,N-butyl methylsulfamate, N,N-dibutylsulfamate Group, N,N-dipentylsulfasulfonyl, N,N-bis(1-ethylpropyl)sulfasulfonyl, N,N-dihexylsulfasulfonyl, N,N-bis(2 -Ethyl) hexylsulfasulfonyl, N,N-diheptylsulfasulfonyl, N,N-octylmethylsulfasulfonyl, N,N-dioctylsulfasulfonyl, N,N -Dinonylsulfasulfonyl, N,N-decylmethylsulfasulfonyl, N,N-undecylmethylsulfasulfonyl, N,N-dodecylmethylsulfasulfonyl, N,N-Eicosyl Methylsulfamate, N,N-Phenyl Methylsulfamate and N,N-Diphenylsulfamate, etc. are substituted by 2 hydrocarbon groups with 1 to 40 carbons The sulfamoyl group, etc., and the sulfamoyl group substituted with 1 or 2 hydrocarbon groups with 1 to 10 carbon atoms are preferred.

-CON(R ¹⁰² ) ₂ includes aminomethyl; N-methylaminomethyl, N-ethylaminomethyl, N-propylaminomethyl, N- Isopropylaminoformyl, N-butylaminoformyl, N-isobutylaminoformyl, N-second butylaminoformyl, N-tertiary butylamino Formyl, N-pentylaminomethanyl, N-(1-ethylpropyl)aminomethanyl, N-hexylaminomethanyl, N-(2-ethyl)hexylamino Formyl, N-heptylaminoformyl, N-octylaminoformyl, N-nonylaminoformyl, N-decylaminoformyl, N-undecylamine Amines substituted by a hydrocarbon group with 1 to 40 carbon atoms such as N-methylamino, N-dodecylaminomethyl, N-eicosylaminomethyl, and N-phenylaminomethyl N,N-dimethylaminomethanyl, N,N-ethylmethylaminomethanyl, N,N-diethylaminomethanyl, N,N- Propylmethylaminomethanyl, N,N-dipropylaminomethanyl, N,N-isopropylmethylaminomethanyl, N,N-diisopropylaminomethanyl Group, N,N-tertiary butylmethylaminomethanyl, N,N-diisobutylaminomethanyl, N,N-disecondbutylaminomethanyl, N,N-di Tertiary butylaminoformyl, N,N-butylmethylaminoformyl, N,N-dibutylaminoformyl, N,N-butyloctylaminoformyl, N , N-dipentylaminomethanyl, N,N-bis(1-ethylpropyl)aminomethanyl, N,N-dihexylaminomethanyl, N,N-di(2 -Ethyl) hexylaminomethanyl, N,N-diheptylaminomethanyl, N,N-dioctylaminomethanyl, N,N-dioctylaminomethanyl, N,N-Dinonylaminomethanyl, N,N-decylmethylaminomethanyl, N,N-undecylmethylaminomethanyl, N,N-dodecylmethan Aminomethyl, N,N-eicosylmethylaminomethyl, N,N-phenylmethylaminomethyl and N,N-diphenylaminomethyl, etc. Two aminomethanyl groups substituted with a hydrocarbon group having 1 to 40 carbons, and an aminomethanyl group substituted with one or two hydrocarbon groups having 1 to 10 carbons, etc. are preferred.

-N(R ¹⁰² ) ₂ includes an amino group; N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group , N-isobutylamino, N-second butylamino, N-tertiary butylamino, N-pentylamino, N-hexylamino, N-(2-ethyl)hexylamine Group, N-heptylamino group, N-octylamino group, N-nonylamino group, N-decylamino group, N-undecylamino group, N-dodecylamino group, N-twenty N,N-dimethylamino, N,N-ethylmethylamino, N, N, N, N, N, N, N, N, N, N, N, and N, N-diethylamino, N,N-propylmethylamino, N,N-dipropylamino, N,N-isopropylmethylamino, N,N-diisopropylamine Group, N,N-tertiary butylmethylamino group, N,N-diisobutylamino group, N,N-di-second butylamino group, N,N-di-tertiary butylamino group, N, N-butylmethylamino, N,N-dibutylamino, N,N-dipentylamino, N,N-bis(1-ethylpropyl)amino, N,N-dihexylamine Group, N,N-bis(2-ethyl)hexylamino, N,N-diheptylamino, N,N-dioctylamino, N,N-dinonylamino, N,N -Decylmethylamino, N,N-undecylmethylamino, N,N-dodecylmethylamino, N,N-eicosylmethylamino, N,N-phenyl Amino groups such as methylamino groups and N,N-diphenylamino groups substituted with 2 hydrocarbon groups with 1 to 40 carbons, etc., and amines substituted with 1 or 2 hydrocarbon groups with 1 to 10 carbons can be cited The base is better.

-NHCO-R ¹⁰² includes formamide; acetamido, acrylamido, butyramido, 2,2-dimethyl propamido, pentamido, and hexamido Group, (2-ethyl) hexamido, heptamido, octamido, nonamido, decamido, undecamido, dodecamido, benziamido A carbonylamino group to which a hydrocarbon group having 1 to 40 carbon atoms is bonded, such as a benzylamino group, and the like, and a carbonylamino group to which a hydrocarbon group having 1 to 10 carbon atoms are bonded are preferable.

The halogen atom is preferably fluorine atom, chlorine atom, bromine atom and iodine atom.

Examples of M of -SO ₃ M and -CO ₂ M include hydrogen atoms; alkali metal atoms such as lithium atoms, sodium atoms, and potassium atoms, and preferably hydrogen atoms, sodium atoms, and potassium atoms.

、N-甲基鄰苯二甲醯亞胺、N-(1-苯基乙基)鄰苯二甲醯亞胺及稠四苯等烴系縮環結構及其部分還原體(例如9,10-二氫蒽、1,2,3,4-四氫萘等)；吲哚、異吲哚、吲唑、喹啉、異喹啉、呔

、喹

啉、喹唑啉、

啉、咔唑、咔啉、菲啶、吖啶、嘧啶、菲羅啉、啡

等含氮縮合雜環及其部分還原體；3-氫苯并呋喃2-酮等含氧縮合雜環及其部分還原體。 The ring formed by R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ^{5 is} condensed with the benzene ring of the isoindoline skeleton of formula (I). The condensed ring structure of the ring formed by R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ and the aforementioned benzene ring, including indene, naphthalene, biphenyl, and dicyclopentacene (indacen) , Acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, acetylanthene, triphenylene, pyrene,

, N-methyl phthalimide, N-(1-phenylethyl) phthalimide and fused tetrabenzene and other hydrocarbon condensed ring structures and their partial reductions (such as 9,10 -Dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, etc.); indole, isoindole, indazole, quinoline, isoquinoline, xanthene

Quine

Quinazoline,

Phenanthroline, carbazole, carboline, phenanthridine, acridine, pyrimidine, phenanthroline, phenanthrene

And other nitrogen-containing condensed heterocycles and their partial reductions; 3-hydrobenzofuran 2-one and other oxygen-containing condensed heterocycles and their partial reductions.

When R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ form a ring, the ring may have a substituent. Examples of the substituent include the same substituents that the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have. Preferred substituents of this substituent include the same groups as the preferred substituents that the hydrocarbon groups represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have.

The ring formed by R ¹² and R ^{13 is} bonded to the exomethylene (C=CH ₂ ) outside the isoindoline skeleton of formula (I). The ring formed by R ¹² and R ¹³ contains other sub In the case of the structure of a methyl group (C=CH ₂ ), a structure in which the carbonyl group and exo-methylene group of the following group A are arranged in this order can be exemplified. * *, the bonding point of the isoindoline skeleton.

[Group A]

R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, Cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or optionally substituted heterocyclic group.

R ¹⁰⁴ and R ¹⁰⁵ are each independently methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl, (2-ethyl)hexyl, heptyl, octyl , Nonyl, cyclohexyl, phenyl and other hydrocarbon groups with 1 to 10 carbon atoms or hydrogen atoms are preferred.

The group exemplified in group A may be substituted with a substituent for the hydrogen atom bonded to the ring structure. Examples of the substituent include the same substituents that the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have.

When R ¹² and R ¹³ do not form a ring, compound (I) is a compound represented by formula (Ia) (hereinafter, also referred to as compound (Ia)), a compound represented by formula (II) (hereinafter, also referred to as In the case of compound (II)), the compound represented by formula (II-a1) (hereinafter, also referred to as compound (II-a1)) is preferred.

In the formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

L ² represents -CO- or -SO ₂ -.

R ¹⁴ represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group.

The hydrocarbon group having 1 to 40 carbon atoms or the heterocyclic group that may have substituents represented by R ¹⁴ and the hydrocarbon group having 1 to 40 carbon atoms or the optionally substituted heterocyclic group represented by R ¹¹ and R ¹⁰¹ The same group as the substituted heterocyclic group.

In compound (Ia), R ¹¹ and R ¹⁴ are preferably the same group. Furthermore, L ¹ and L ² are preferably on the same base.

R ¹¹ and R ¹⁴ are each independently, preferably phenyl which may have a substituent, naphthyl which may have a substituent, tetrahydronaphthyl which may have a substituent, pyridyl which may have a substituent, Substituent thienyl group, optionally substituted furyl group, or optionally substituted alkyl group. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 8.

The substituents of phenyl, naphthyl, tetrahydronaphthyl, thienyl, furanyl and pyridyl are based on methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, (2 -Ethyl) hexyl and octyl and other C1-C10 alkyl groups; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; trifluoromethyl group; oxygen bonded to a C1-C10 hydrocarbon group Carbonyl; Nitro; Hydroxyl; Sulfamidine; -SO ₃ M; -CO ₂ M is preferred.

The substituents of the alkyl group are preferably halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; -SO ₃ M; -CO ₂ M.

L ¹ is preferably -CO-.

L ² is preferably -CO-.

R ^{1 is} preferably a hydrogen atom.

R ² to R ⁵ are preferably each independently a hydrogen atom, a halogen atom or a nitro group. The halogen atom is preferably a fluorine atom, a chlorine atom and a bromine atom, and more preferably a chlorine atom. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

In the formula (II), R ¹ to R ⁵ and R ¹¹ to R ¹³ respectively represent the same meaning as described above.

R ¹¹ is a substituted phenyl group, optionally substituted naphthyl group, optionally substituted tetrahydronaphthyl group, optionally substituted pyridyl group, optionally substituted thienyl group, optionally substituted The furyl group or the alkyl group which may have a substituent is preferable. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 8.

The substituents of phenyl, naphthyl, tetrahydronaphthyl, thienyl, furanyl and pyridyl are based on methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, (2 -Ethyl) hexyl and octyl and other C1-C10 alkyl groups; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; trifluoromethyl group; oxygen bonded to a C1-C10 hydrocarbon group Carbonyl; Nitro; Hydroxyl; Sulfamidine; -SO ₃ M; -CO ₂ M is preferred.

As for the substituent of the alkyl group, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; -SO ₃ M; -CO ₂ M are preferred.

R ^{1 is} preferably a fluorine atom.

R ² to R ⁵ are preferably each independently a hydrogen atom, a halogen atom or a nitro group. The halogen atom is preferably a fluorine atom, a chlorine atom and a bromine atom, and more preferably a chlorine atom. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

R ¹² is preferably -CO-R ¹⁰² or -SO ₂ -R ¹⁰¹ . R ¹² is preferably -CO-R ¹⁰² .

R ¹³ is preferably a cyano group.

R ¹⁰¹ and R ¹⁰² respectively mean the same as the above.

In the formula (II-a1), R ¹ to R ⁵ , R ¹² to R ¹³ and the wavy line respectively represent the same meaning as described above. R ¹¹¹ is a heterocyclic ring which may have a substituent, and R ¹¹¹ is a heterocyclic ring which may have a substituent, or a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent. However, when R ¹¹¹ is a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, any one of R ¹² and R ¹³ is -SO ₂ -R ¹¹¹ , and the other of R ¹² and R ¹³ is a cyano group, At least one of R ² to R ⁵ represents -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, A nitro group, -SO ₃ M, -CO ₂ M, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, or an optionally substituted heterocyclic group.

R ¹¹¹ represents a heterocyclic group of the substituent group, represented by R ¹¹ include the same optionally substituted heterocyclic ring may have a group of persons.

R ¹¹¹ is preferably pyridyl, thienyl and furyl which may have a substituent.

Substituents of thienyl, furanyl and pyridyl, based on the carbon number of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, (2-ethyl)hexyl and octyl Alkyl group of 1 to 10; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; trifluoromethyl group; oxycarbonyl group bonded to a hydrocarbon group with 1 to 10 carbon atoms; nitro group; hydroxyl group; sulfasulfonyl group ; -SO ₃ M; -CO ₂ M is better.

R ¹² is preferably -CO-R ¹⁰² or -SO ₂ -R ¹⁰¹ . R ¹² is preferably -SO ₂ -R ¹⁰¹ . R ¹⁰¹ and R ¹⁰² respectively mean the same as the above.

R ¹³ is preferably a cyano group.

R ^{1 is} preferably a hydrogen atom.

R ² to R ⁵ are preferably each independently a hydrogen atom, a halogen atom or a nitro group. The halogen atom is preferably a fluorine atom, a chlorine atom and a bromine atom, and more preferably a chlorine atom. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

In the compound (II-a1), the above-mentioned hydrocarbon groups include the hydrocarbon groups exemplified in R ¹¹ .

When R ¹² and R ¹³ form a ring, compound (I) is preferably a compound represented by formula (Ib) (hereinafter, it may also be referred to as compound (Ib)).

In the formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

R ²⁰ and R ³⁰ are bonded to form ring Q.

The ring Q may have a substituent and a ring having 5 to 7 ring members. The ring Q may be a hydrocarbon ring or a heterocyclic ring. In ring Q, selectable by bonding A monocyclic ring composed of 5 to 7 members from a hydrocarbon ring and a heterocyclic ring, or a condensed ring formed by condensation of the monocyclic ring.

The number of members of the ring is preferably from 5 to 6.

These monocyclic rings or condensed rings are preferably bonded to ring Q at two places to form condensed rings.

Regarding the ring Q and the ring to which a monocyclic ring or a condensed ring is bonded, the same formula (QQ1) to formula (QQ25) as the aforementioned group A can be cited.

Among them, formula (Q1), formula (Q4), formula (Q7), formula (Q8), formula (Q18), formula (QQ5), formula (QQ9), formula (QQ25) are preferred, and formula (Q8) , Formula (Q18), formula (QQ9), formula (QQ25) are better.

The compound (I-b) is more preferably a compound represented by formula (I-c) (hereinafter, it may also be referred to as compound (I-c)).

In the formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line have the same meaning as described above.

R ⁶ and R ⁷ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, Cyano group, nitro group, -SO ₃ M, -CO ₂ M, or a hydrocarbon having 1 to 40 carbon atoms which may have a substituent or a heterocyclic ring which may have a substituent.

R ¹⁰¹ , R ¹⁰² and M have the same meaning as above.

In compound (Ib) and compound (Ic), R ¹¹ is a substituted phenyl group, optionally substituted naphthyl group, optionally substituted tetrahydronaphthyl group, optionally substituted pyridyl group, The thienyl group which may have a substituent, the furyl group which may have a substituent, or the alkyl group which may have a substituent is preferable.

When R ¹¹ is an optionally substituted alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms.

The substituents of phenyl, naphthyl, tetrahydronaphthyl, thienyl, furanyl and pyridyl are based on methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, (2 -Ethyl) hexyl and octyl and other C1-C10 alkyl groups; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; trifluoromethyl group; oxygen bonded to a C1-C10 hydrocarbon group Carbonyl; Nitro; Hydroxyl; Sulfamidine; -SO ₃ M; -CO ₂ M is preferred.

The substituents of the alkyl group are preferably halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; -SO ₃ M; -CO ₂ M.

R ^{1 is} preferably a hydrogen atom. L ¹ is preferably -CO-.

R ² to R ⁵ are preferably each independently a hydrogen atom, a halogen atom or a nitro group. The halogen atom is preferably a fluorine atom, a chlorine atom and a bromine atom, and more preferably a chlorine atom. The number of halogen atoms is preferably 1 to 4, more preferably 1 to 2. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

R ⁶ and R ⁷ are each independently methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, (2-ethyl)hexyl, octyl, etc. with carbon numbers from 1 to 10 The alkyl group, cycloalkyl group, phenyl group or hydrogen atom is preferred.

Specific examples of the compound (I) include, for example, compounds (compounds 1 to 360 and compounds 725 to 745) having the substituents shown in Table 1 to Table 4 and Table 9(a) in formula (I-aa). B ¹ B ² represents any structure represented by formula (BB1) to formula (BB60). R ¹¹ and R ¹⁴ represent any structure represented by formula (HH1) to formula (HH89).

Furthermore, specific examples of compound (I) include, for example, in formula (I-bb), compounds having substituents shown in Tables 5 to 8 and Table 9(b) (compounds 361 to 724 and compounds 746 to 759). B ¹ B ² represents any structure represented by formula (BB1) to formula (BB60). QQ means any structure represented by formula (QQ1) to formula (QQ25). R ¹¹ represents any structure represented by formula (HH1) to formula (HH89).

Specific examples of the compound (I) include compounds in which 1 to 3 -SO ₃ M or -CO ₂ M are bonded among the compounds shown in Table 1 to Table 9(a) and Table 9(b). For example, in the compound 102 of Table 2, the compound with 1 to 3 sulfonic acid groups bonded has the following structure.

As far as the ease of synthesis is low, compound 1 to compound 12, compound 100 to compound 273, compound 448 to compound 637, compound 725 to compound 759, and any of these compounds are bonded with 1 to 3 A compound of -SO ₃ M or -CO ₂ M is preferably compound 1 to compound 12, compound 100 to compound 168, compound 186 to compound 255, compound 273, compound 448 to compound 532, compound 550 to compound 619, compound 637, compound 725 to compound 726, compound 732 to compound 733, compound 739 to compound 740, compound 746 to compound 747, compound 753 to compound 754, and any of these compounds are bonded with 1 to 3 -SO Compounds of ₃ M or -CO ₂ M are more preferred; compound 100 to compound 168, compound 186 to 255, compound 273, compound 464 to compound 532, compound 550 to compound 619, compound 637, compound 732 to compound 733, compound 739 It is particularly preferred to compound 740, compound 746 to compound 747, compound 753 to compound 754, and any of these compounds to which 1 to 3 -SO ₃ M or -CO ₂ M are bonded.

The symbols in Tables 1 to 9(b) indicate the following structures. In the following structure, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. At the same time, *, B ¹ , B ² and * * indicate the bonding location respectively.

For compound (I), in formula (I), L ¹ is -CO- or -SO ₂ -, preferably -CO-, R ¹ is a hydrogen atom or -SO ₃ M, R ² to R ⁵ , which are independently hydrogen atom, nitro group, -SO ₃ M or halogen atom, R ¹¹ , may have a group selected from -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -SO ₃ M, -CO ₂ M, -OR ¹⁰² , -SO ₂ N(R ¹⁰² ) ₂ , a halogen atom, a cyano group and a nitro group formed by the substituent group is an aromatic hydrocarbon group having 6 to 10 carbon atoms, one of R ¹² and R ¹³ Is a cyano group, the other of R ¹² and R ¹³ is a group represented by -CO-R ¹¹ or -SO ₂ -R ¹¹ , preferably a group represented by -CO-R ¹¹ , and R ¹⁰¹ and R ¹⁰² are respectively A hydrogen atom or an aliphatic hydrocarbon group with 1 to 8 carbon atoms, M is preferably a compound of a hydrogen atom or an alkali metal atom, preferably L ¹ , -CO- or -SO ₂ -, preferably -CO-, R ^1. It is a hydrogen atom or -SO ₃ M, R ² to R ⁵ are each independently a hydrogen atom, a nitro group, -SO ₃ M or a halogen atom, and R ¹¹ may be selected from -COO-R ¹⁰¹ ,- The phenyl group of the substituent in the group formed by OCO-R ¹⁰² , -SO ₃ M, -CO ₂ M, -OR ¹⁰² , -SO ₂ N(R ¹⁰² ) ₂ , halogen atom, cyano group and nitro group, One of R ¹² and R ¹³ is a cyano group, and the other of R ¹² and R ¹³ is a group represented by -CO-R ¹¹ or -SO ₂ -R ¹¹ , preferably -CO-R ¹¹ , and R ¹⁰¹ and R ¹⁰² are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and M is a compound in which a hydrogen atom or an alkali metal atom is more preferred.

Preferred compound (I), in addition to the above-mentioned compounds, includes compounds represented by formula (Ic), wherein L ¹ is -CO- or -SO ₂ -, preferably -CO-, and R ¹ is a hydrogen atom or -SO ₃ M, R ² to R ⁵ are independently hydrogen atom, nitro group, -SO ₃ M or halogen atom, R ⁶ to R ⁷ are independently hydrogen atom, -SO ₃ M, carbon number 1 To 4 alkyl, carbon 3 to 8 cycloalkyl or phenyl, R ¹¹ may be selected from -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -SO ₃ M, -CO ₂ M,- The substituent in the group formed by OR ¹⁰² , -SO ₂ N(R ¹⁰² ) ₂ , halogen atom, cyano group and nitro group is an aromatic hydrocarbon group with 6 to 10 carbon atoms, and M is a hydrogen atom or an alkali metal atom.

Compound (I), when R ¹ is a hydrogen atom, the compound represented by formula (pt1) (hereinafter, also referred to as phthalonitrile compound) and the compound represented by formula (pt2) (hereinafter, also referred to as (In the case of alcohol oxide) After the reaction, it is produced by reacting with the compound represented by formula (pt3) and the compound represented by formula (pt4) in the presence of an acid. When R ¹ is other than a hydrogen atom, the compound (I) can be produced by reacting with the compound represented by formula (pt5).

In formula (pt1) to formula (pt5) and formula (I), R ¹ to R ⁵ and R ¹¹ to R ^{13 have the} same meaning as described above. R ¹⁴ represents an alkyl group having 1 to 20 carbons.

M ¹ represents an alkali metal atom. LG means halogen atom, methanesulfonyloxy group, toluenesulfonyloxy group or trifluoromethanesulfonyloxy group.

The alkyl group having 1 to 20 carbons represented by R ¹⁴ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tertiary butyl, etc. The number of carbons is An alkyl group of 1 to 6 is preferred.

The alkali metal atom represented by M ¹ includes a lithium atom, a sodium atom, and a potassium atom.

Relative to 1 mol of the phthalonitrile compound, the usage amount of the alcohol oxide compound is usually 0.1 to 10 mol, preferably 0.2 to 5 mol, more preferably 0.3 to 3 mol, and 0.4 to 2 mol. Better.

Relative to 1 mol of the phthalonitrile compound, the usage amount of the compound (pt3) is usually 1 to 10 mol, preferably 1 to 5 mol, more preferably 1 to 3 mol, and 1 to 2 mol. Better.

Relative to 1 mole of phthalonitrile compound, the amount of compound (pt4) used is generally It is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles, and even more preferably 1 to 2 moles.

As for the acid, inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, fluorosulfonic acid, phosphoric acid, etc.; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid; acetic acid, Carboxylic acids such as citric acid, formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and carboxylic acid, more preferably It is acetic acid.

Relative to 1 mole of the phthalonitrile compound, the amount of acid used is usually 1 to 20 moles, preferably 1 to 10 moles, more preferably 1 to 8 moles, and more preferably 1 to 6 moles .

The reaction of the phthalonitrile compound, alcohol oxide compound, compound (pt3), and compound (pt4) is usually carried out in the presence of a solvent.

Solvents include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; Ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as dichloromethane and chloroform; N,N-dimethylformaldehyde and N-methylpyrrolidone Amine solvents; sulfite solvents such as dimethyl sulfite, preferably water, nitrile solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amine solvents and sulfite solvents , More preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, methylene chloride, chloroform, N , N-dimethylformaldehyde, N-methylpyrrolidone and dimethyl sulfoxide, more preferably water, acetonitrile, methanol, Ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, dichloromethane, chloroform, N,N-dimethylformaldehyde, N-methylpyrrolidone and dimethyl Subsoil, particularly preferably water, acetonitrile, methanol, ethanol and 2-propanol.

The amount of the solvent used is usually 1 to 1000 parts by mass relative to 1 part by mass of the phthalonitrile compound.

The reaction temperature is usually 0 to 200°C, preferably 0 to 100°C, and more preferably 0 to 50°C. The reaction time is usually 0.5 to 300 hours.

Relative to 1 mol of compound (I) where R ¹ is a hydrogen atom, the amount of compound (pt5) used is usually 1 to 10 mol, preferably 1 to 5 mol, and more preferably 1 to 3 mol, It is better to use 1 to 2 moles.

Furthermore, when reacting the compound (pt5), it is preferable to coexist with a base. The base includes organic bases such as triethylamine, 4-(N,N-dimethylamino)pyridine, pyridine, and piperidine, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, etc. Organometallic compounds such as metal alcohol oxides, butyl lithium, tertiary butyl lithium and phenyl lithium; inorganic bases such as lithium hydroxide, sodium hydroxide and potassium hydroxide.

Relative to 1 mole of compound (I) in which R ¹ is a hydrogen atom, the amount of base used is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles, and 1 to 10 moles. 2Mole is better.

The reaction of the compound (pt5) is usually carried out in the presence of a solvent. The solvent can be selected from the same range as described above.

The amount of solvent used is usually 1 to 1000 parts by mass relative to 1 mole of compound (I) in which R ¹ is not a hydrogen atom. The reaction temperature of the compound (pt5) is usually -90 to 200°C, preferably -80 to 100°C, and more preferably 0 to 50°C. The reaction time is usually 0.5 to 300 hours.

When the compound (I) does not have a sulfonic acid group, the sulfonic acid group can be introduced by reacting the compound (I) with a sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid.

Relative to 1 mole of compound (I), the usage amount of SO _{3 in} fuming sulfuric acid is usually 1 to 50 moles, preferably 5 to 40 moles, more preferably 5 to 30 moles, and 5 to 30 moles. 25 moles is better.

Relative to 1 mole of compound (I), the amount of sulfuric acid used in fuming sulfuric acid is usually 1 to 200 moles, preferably 10 to 100 moles, more preferably 10 to 75 moles, and 10 to 50 moles. Moer is better.

Relative to 1 mol of compound (I), the usage amount of chlorosulfonic acid is usually 1 to 500 mol, preferably 10 to 300 mol, more preferably 10 to 200 mol, and 10 to 150 mol. Better.

The reaction temperature of sulfonation is usually -20 to 200°C, preferably -10 to 100°C, and more preferably 0 to 50°C. The reaction time is usually 0.5 to 300 hours.

The method of taking out the compound (I) from the reaction mixture is not particularly limited, and it can be taken out by a known method. For example, after the reaction is completed, by filtering the reaction mixture, compound (I) can be taken out. Furthermore, after filtration, the obtained residue may be subjected to column chromatography or recrystallization. In addition, after the reaction is completed, the solvent of the reaction mixture is distilled off, and then purified by column chromatography.

The coloring composition of the present invention contains compound (I) and resin (B). Compound (I) can be used as a colorant.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin and has a monomer (a) derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter also referred to as " (a) "In the case of "), the polymer of the structural unit is more preferable.

Resin (B) is one of the structural units derived from monomer (b) (hereinafter also referred to as "(b)") having a cyclic ether structure with carbon number 2 to 4 and an ethylenically unsaturated bond Copolymer is preferred.

Other structural units include monomers (c) that can be copolymerized with monomer (a) (but are different from monomers (a) and monomers (b). Hereinafter, it is also referred to as "( c) "In the case of) the structural unit, the structural unit with ethylenically unsaturated bond, etc.

(a) Examples include: for example, acrylic acid, methacrylic acid, crotonic acid, and unsaturated monocarboxylic acids such as ortho-, meta-, and p-vinyl benzoic acid; maleic acid, fumaric acid , Citraconic acid, mesaconic acid, itaconic acid, 3-ethylene phthalic acid, 4-ethylene phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3, Unsaturated dicarboxylic acids such as 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-di Carboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxymethylbicyclo[2.2.1] Bicyclic unsaturated compounds containing carboxyl groups such as hept-2-ene and 5-carboxyethylbicyclo[2.2.1]hept-2-ene; the above-mentioned unsaturated dicarboxylic acids other than maleic acid and mesaconic acid Carboxylic acid anhydrides such as acid anhydrides; succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono [2-(Meth)acryloyloxyethyl] and other unsaturated mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids with more than two valences; such as α-(hydroxymeth)acrylic acid The unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

Among these monomers, acrylic acid, methacrylic acid, and maleic anhydride are preferred in terms of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(b) It refers to a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an ethylene oxide ring, a butylene oxide ring and a tetrahydrofuran ring) and ethylenically unsaturated Bond polymerizable compound. (b) It is preferably a cyclic ether having 2 to 4 carbon atoms and a monomer having a (meth)acryloxy group.

For (b), for example, monomers (b1) having ethylene oxide groups and ethylenically unsaturated bonds (hereinafter also referred to as "(b1)"), butylene oxide groups and ethylenic Monomer with unsaturated bond (b2) (hereinafter also referred to as "(b2)") and monomer with tetrahydrofuran group and ethylenically unsaturated bond (b3) (hereinafter also referred to as "(b3)" )Wait.

For (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter also referred to as "(b1-1)" Case) and a monomer (b1-2) having an epoxidized structure of alicyclic unsaturated hydrocarbon (hereinafter also referred to as "(b1-2)").

(b1-1) Preferably, it is a monomer having a glycidyl group and an ethylenically unsaturated bond. (b1-1) Specific examples include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β-ethylglycidyl (meth) Acrylate, glycidyl vinyl ether, vinyl benzyl glycidyl ether, α-methyl vinyl benzyl glycidyl ether, 2,3-bis(glycidoxymethyl) Styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl) )Styrene, 2,3,4-gin (glycidoxymethyl) styrene, 2,3,5-gin (glycidoxymethyl) styrene, 2,3,6-gin ( Glycidoxymethyl)styrene, 3,4,5-gins(glycidoxymethyl)styrene and 2,4,6-gins(glycidoxymethyl)styrene, etc.

(b1-2) Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE (registered trademark) 2000; Daicel Co., Ltd.) , 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel (stock)), 3,4-epoxycyclohexyl methyl (meth)acrylate Base ester (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Co., Ltd.), a compound represented by formula (BI), a compound represented by formula (BII), and the like.

Formula (BI) and the formula (BII), R ^a is and R ^b, independently represent a line a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, the hydrogen atoms contained in the alkyl group, a hydroxyl group may also be substituted. X ^a and X ^b, each independently represent a single bond ^{lines, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-. R ^{c is} an alkanediyl group having 1 to 6 carbon atoms. ＊Denotes the bond with O.

The compound represented by formula (BI) includes compounds represented by any of formula (BI-1) to formula (BI-15), and the like. Among them, according to formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), and formula (BI-11) to formula (BI-15) are preferably compounds represented by formula (BI-1), formula (BI -7) The compounds represented by formula (BI-9) and formula (BI-15) are more preferable.

The compound represented by formula (BII) includes compounds represented by any of formula (BII-1) to formula (BII-15), etc., among which formula (BII-1), formula (BII-3), and formula (BII-5), formula (BII-7), formula (BII-9), and formula (BII-11) to formula (BII-15) are preferably compounds represented by formula (BII-1), formula ( The compounds represented by BII-7), formula (BII-9) and formula (BII-15) are more preferred.

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone, respectively, or the compound represented by the formula (BI) may be used in combination with the compound represented by the formula (BII). When these compounds are used in combination, when the content ratio of the compound represented by formula (BI) and the compound represented by formula (BII) is based on moles, it is preferably 5:95 to 95:5, preferably 10:90 to 90:10 is better, and 20:80 to 80:20 is even better.

(c) Examples include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, (meth)acrylic acid Tertiary butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Cyclopentyl ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]dec-8-yl ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]dec-9-yl ester, (form (Base) tricyclic [5.2.1.0 ^2,6 ] decene-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-9-yl (meth)acrylate, di (meth) acrylate Cyclopentadiyloxyethyl ester, isonorbornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, (meth)propargyl (Meth)acrylates such as phenyl acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate and 2-hydroxy (meth)acrylate (Meth)acrylates containing hydroxyl groups such as propyl ester; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; bicyclic [2.2. 1]Hept-2-ene, 5-methyl bicyclic [2.2.1]hept-2-ene, 5-ethyl bicyclic [2.2.1]hept-2-ene, 5-hydroxy bicyclic [2.2. 1]Hept-2-ene, 5-hydroxymethyl bicyclic [2.2.1]hept-2-ene, 5-(2'-hydroxyethyl) bicyclic [2.2.1]hept-2-ene, 5 -Methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept- 2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicycle[2.2.1]hept-2 -Ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5 -Methyl bicyclic[2.2.1]hept-2-ene, 5-hydroxy-5-ethyl bicyclic[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl bicyclic[ 2.2.1]Hept-2-ene, 5-tertiary butoxycarbonyl bicyclic [2.2.1]hept-2-ene, 5-cyclohexoxycarbonyl bicyclic [2.2.1]hept-2-ene , 5-phenoxycarbonyl bicyclic [2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl) bicyclic [2.2.1]hept-2-ene and 5,6- Bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide , N-benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide Imine Butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N-(9 -Acridinyl) maleimide and other dicarbonyl amide derivatives; styrene, α-methylstyrene, vinyl toluene and p-methoxystyrene and other aromatic compounds containing vinyl groups; Vinyl-containing nitriles such as (meth)propionitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; (meth)acrylamide and other vinyl-containing amides; vinyl acetate and other esters; 1,3-butane Diene, isopentene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, (meth)acrylic tricyclo[5.2.1.0 ^2,6 ]dec-8-yl ester, (methyl) )Acrylic tricyclo[5.2.1.0 ^2,6 ]dec-9-yl ester, (meth)acrylic tricyclo[5.2.1.0 ^2,6 ]decene-8-yl ester, (meth)acrylic tricyclo[ 5.2.1.0 ^2,6 ]decene-9-yl ester, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide Amine, bicyclo[2.2.1]hept-2-ene, and benzyl (meth)acrylate are preferred.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. A resin having such a structural unit can be added to a polymer having a structural unit derived from (a) and (b), and a group that can react with the group having (a) or (b) is added to have an ethylenic property Derived from monomers with unsaturated bonds.

Such structural unit may include adding (meth)acrylic acid unit to (meth) The structural unit of glycidyl acrylate, the structural unit of 2-hydroxyethyl (meth)acrylate is added to the maleic anhydride unit, and the (methyl) is added to the glycidyl (meth)acrylate unit The structural unit of acrylic acid, etc. In addition, when these structural units have a hydroxyl group, a structural unit to which a carboxylic anhydride is further added can also be cited as a structural unit having an ethylenically unsaturated bond.

The polymer having the structural unit derived from (a) can be produced, for example, by polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent, etc. are not particularly limited, and users usually in the field can be used.

For example, the polymerization initiator includes azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic Peroxide (benzyl peroxide, etc.); as far as the solvent is concerned, any monomer can be dissolved.

In addition, the obtained polymer may be directly used as a solution after the reaction, a concentrated or diluted solution may be used, or a solid (powder) obtained by reprecipitation or the like may be used.

If necessary, a reaction catalyst of a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, ginseng (dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) may also be used.

For carboxylic anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-ethylene phthalic anhydride, 4-ethylene phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxyl bicyclic [2.2.1]hept-2-ene Anhydride etc.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, and 3,4-epoxy tricyclic (meth)acrylate [ 5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid Glycidyl ester/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-ring Hexyl maleimide copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexyl maleic acid Amide/2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylate 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/ethylene Toluene copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/(meth)acrylic acid 2-ethylhexyl copolymer, ( 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decenyl (meth)acrylate/tricyclo[5.2.1.0 ^2,6 ]decenyl(meth)acrylate/(meth)acrylic acid/ N-cyclohexyl maleimide copolymer, 3-methyl-3-(meth)acryloyloxymethylbutylene oxide/(meth)acrylic acid/styrene copolymer, (methyl) ) Benzyl acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, and Japanese Patent Application Publication No. 9-106071, Japanese Patent Application Publication No. 2004-29518, and Japanese Patent Application Publication No. 2004-361455 The resins described in the bulletins of the No. Bulletin.

Among them, the resin (B) is preferably a copolymer containing a structural unit derived from (a) and a structural unit derived from (b).

The resin (B) can be a combination of two or more types. In this case, the resin (B) contains 3,4-epoxy tricyclic [5.2.1.0 ^2,6 ] decyl ester/( Meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide/ 2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/ethylene toluene copolymer, At least one of 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer Better.

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

The acid value (converted value of solid content) of the resin (B) is preferably 10 to 300 mg-KOH/g, more preferably 20 to 250 mg-KOH/g, and more preferably 20 to 200 mg-KOH/g. 20 to 170 mg-KOH/g is even more preferable, 30 to 170 mg-KOH/g is very preferable, 60 to 150 mg-KOH/g is even better, and 70 to 135 mg-KOH/g is particularly preferable. The acid value here is a value for measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

In the coloring composition, relative to the total solid content, the content of resin (B) is preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably 7 to 99% by mass, and 13 It is more preferably to 99% by mass, particularly preferably from 17 to 95% by mass.

The "total amount of solid content" in this specification refers to the total amount of the components after removing the solvent (E) from the coloring composition of the present invention. The total amount of solid content and the relative content of each component can be determined by known analytical methods such as liquid chromatography or gas chromatography.

<Colorant (A1)>

The coloring composition of the present invention may contain a coloring agent other than the compound (I) (hereinafter, it may also be referred to as a coloring agent (A1)). The coloring agent (A1) may contain one or more coloring agents. The colorant (A1) preferably contains a yellow colorant or a green colorant.

The colorant (A1) may be a dye or a pigment. The dyes include known dyes described in the Color Index (published by The Society of Dyers and Colourists) and Dyeing Notes (Sei Dyers). Furthermore, depending on the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, phthalocyanine dyes, and the like can be cited. Two or more of these dyes may be used in combination.

Specifically, dyes with the following color index (C.I.) numbers can be cited.

CI solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; 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 Reactive Yellow 2, 76, 116; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Disperse Yellow 51, 54, 76; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI Lime 6 , 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Reactive Orange 16; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Solvent Red 24, 49, 90, 91, 111,118,119,122,124,125,127,130,132,143,145,146,150,151,155,160,168,169,172,175,181,207,218,222,227, 230, 245, 247; CI Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 34, 102; CI Disperse Violet 26, 27; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68 , 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; CI Direct Blue 40; CI Disperse Blue 1, 14, 56, 60; C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; C.I. Acid Green 3, 5, 9, 25, 27, 28, 41; C.I. Basic Green 1; C.I. Bat Green 1, etc.

As for the pigment, known pigments can be used, for example, pigments classified in pigments in the color index (published by The Society of Dyers and Colourists). Two or more types can also be combined.

Specifically, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 can be cited , 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51 , 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209 , 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments ; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments.

The colorant (A1) includes yellow dyes and yellow pigments (hereinafter, these are collectively referred to as "yellow colorants"), green dyes and green pigments (hereinafter, these are also collectively referred to as "green colorants" It is better to use yellow pigments and green pigments, and even better to use green pigments.

The yellow dyes include those whose hue is classified as yellow among the above-mentioned dyes; and the yellow pigments include those whose hue is classified as yellow among the above-mentioned pigments.

Among the yellow pigments, quinolinone yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments are preferred.

The green dyes include those whose hue is classified as green among the above-mentioned dyes; and the green pigments include those whose hue is classified as green among the above-mentioned pigments.

Among the green pigments, phthalocyanine pigments are preferred, and at least one selected from the group formed by halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferred, and is selected from CI Pigment Green 7, 36, 58 and At least one of the group formed by 59 is even better.

<Solvent (E)>

The coloring composition may contain a solvent (E). The solvent (E) includes, for example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule, no -O-, -CO- And -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide, etc.

The ester solvent includes methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯乙醚及甲基苯甲醚等。 Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene two Alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, Tetrahydropyran, 1,4-bis

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenylethyl ether and Methyl anisole and so on.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Ester, 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 And dipropylene glycol methyl ether acetate and so on.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone , Cyclopentanone, cyclohexanone and isophorone, etc.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

Aromatic hydrocarbon solvents, including benzene, toluene, xylene, mesitylene Wait.

The amide solvent includes N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

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

Relative to the total amount of the coloring composition, the content of the solvent (E) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass, more preferably 70 to 95% by mass, and more preferably 75 to 90% by mass It's even better.

When the coloring composition of the present invention contains a solvent (E), it can also be prepared by using a coloring agent-containing liquid containing compound (I) or a coloring agent (A1) and a solvent (E) beforehand. Coloring composition. When the colorant is not dissolved in the solvent (E), the colorant-containing liquid can be prepared by dispersing and mixing the coloring agent in the solvent (E). The colorant-containing liquid may contain part or all of the solvent (E) contained in the coloring composition.

The above-mentioned coloring composition is preferably obtained by combining the compound represented by formula (I), resin (B), optionally used solvent (E), and coloring agent (A1) containing colorant (A1) and solvent (E) It is produced by mixing containing liquid. In the aforementioned production method, it is preferable to mix the compound represented by the formula (I), the resin (B), and the solvent (E) as necessary by a bead mill, and to mix the resulting mixture with the colorant (A1) and The coloring agent (A1) of the solvent (E) contains a liquid mixing method.

The coloring agent (A1) preferably contains one or more coloring agents selected from a green coloring agent and a yellow coloring agent.

Coloring agents such as compound (I) can also be treated with rosin, surface treatment using coloring agent derivatives introduced with acidic or basic groups, etc., grafting treatment on the surface of the coloring agent via polymer compounds, etc. via Microparticulation treatment such as sulfuric acid microparticulation method, washing treatment through organic solvents or water for removing impurities, removal treatment through ion exchange method of ionic impurities, etc. The particle size of the colorant is preferably approximately uniform. The colorant can be dispersed by containing a dispersant, so that the colorant can be uniformly dispersed in the dispersion. The colorant may be separately subjected to a dispersion treatment, or several types may be mixed and subjected to a dispersion treatment.

As for the dispersant, surfactants and the like can be cited, and any of cationic, anionic, nonionic, and amphoteric surfactants can be used. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants, etc. can be cited. These dispersants can be used alone or in combination of two or more kinds. When the dispersant is expressed by a trade name, it may include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), and EFKA (registered Trademark) (BASF (stock) system), Ajisper (registered trademark) (Ajinomoto Precision Technology Co., Ltd.), Disperbyk (registered trademark) (BYK Chemie Co., Ltd.), BYK (registered trademark) (BYK Chemie Co., Ltd.) Wait.

When a dispersant is used to prepare the colorant-containing liquid, the amount of the dispersant (solid content) used is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the colorant. Part by mass or more and 100 parts by mass or less is more preferable, and more preferably 5 parts by mass or more and 50 parts by mass or less. When the amount of the dispersant used is in the aforementioned range, there is a tendency to obtain a coloring agent-containing liquid having a more uniform dispersion state.

The content rate of the coloring agent in the coloring agent-containing liquid is usually 0.1 to 60% by mass of the total amount of the coloring agent-containing liquid, preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass.

In the colorant-containing liquid, relative to the total solid content, the content of the colorant is usually 1% by mass to 90% by mass, preferably 1% by mass to 80% by mass, and 2% by mass to 75% by mass The following is more preferable, and it is still more preferable that it is 5 mass% or more and 75 mass% or less.

After preparing a coloring agent-containing liquid containing a colorant and a solvent (E) in advance, when using the coloring agent-containing liquid to prepare the coloring composition of the present invention, the coloring agent-containing liquid may contain the resin (B) contained in the coloring composition in advance. ) Part or all of it, preferably a part in advance. By containing the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved.

The content of the resin (B) in the colorant-containing liquid is, for example, 1 to 500 parts by mass, preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass relative to 100 parts by mass of the colorant.

In the coloring composition, the total content of the coloring agent (A) of the compound (I) and the coloring agent (A1) relative to the total solid content is usually 1% by mass to 90% by mass, and 1% by mass or more It is preferably 80% by mass or less, more preferably 2% by mass or more and 75% by mass or less, and more preferably 5% by mass or more and 75% by mass or less.

In the total amount of the coloring agent (A), the content of the compound (I) is usually 0.001% by mass or more, preferably 0.003% by mass or more, more preferably 0.005% by mass or more, and more preferably 1% by mass or more. The upper limit is 100% by mass or less, preferably 99.999% by mass or less, more preferably 99.997% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less.

In the total amount of the yellow colorant, the content of the compound (I) is usually 0.001% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more, It is more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit is 100% by mass or less, preferably 99.999% by mass or less, and more preferably 99.997% by mass or less.

When the colorant (A1) is contained, relative to 100 parts by mass of the compound (I), the content of the colorant (A1) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and more preferably 1 part by mass or more , Preferably 10,000 parts by mass or less, more preferably 5,000 parts by mass or less.

The colored curable resin composition of the present invention contains a compound (I), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound polymerized by the active radical and/or acid generated by the polymerization initiator (D), such as a compound having a polymerizable ethylenic unsaturated bond, etc., with (meth)acrylic acid Ester compounds are preferred.

For the polymerizable compound having one ethylenically unsaturated bond, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol Acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and the above-mentioned monomer (a), monomer (b), and monomer (c).

The polymerizable compound having two ethylenically unsaturated bonds includes, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(methyl) ) Acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

Among them, the polymerizable compound (C) has 3 or more ethylenic compounds A polymerizable compound with a saturated bond is preferred. Such polymerizable compounds include, for example, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, and dineopentaerythritol Alcohol penta (meth) acrylate, dineopentaerythritol hexa (meth) acrylate, trineopentaerythritol octa (meth) acrylate, trineopentaerythritol hepta (meth) acrylate, four new Pentaerythritol deca(meth)acrylate, tetraneopentaerythritol non(meth)acrylate, ginseng (2-(meth)acryloxyethyl) isocyanurate, ethylene glycol modified Neopentyl erythritol tetra (meth) acrylate, ethylene glycol modified dineopentaerythritol hexa (meth) acrylate, propylene glycol modified neopentyl erythritol tetra (meth) acrylate, propylene glycol modified two Neopentaerythritol hexa (meth) acrylate, caprolactone modified neopentyl erythritol tetra (meth) acrylate and caprolactone modified dineopentaerythritol hexa (meth) acrylate, etc. Neopentylerythritol penta(meth)acrylate and dineopentaerythritol hexa(meth)acrylate are preferred.

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.

In the colored curable resin composition, relative to the total solid content, the content of the polymerizable compound (C) is preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 5% by mass or more, It is more preferably 7 to 65% by mass or more, even more preferably 13 to 60% by mass or more, and particularly preferably 17 to 55% by mass or more.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acid, etc. by the action of light or heat to start polymerization, and known polymerization initiators can be used.

化合物及醯基膦鎓氧化物化合物等。 The polymerization initiator (D) includes O- oxime compounds, alkyl phenone compounds, biimidazole compounds, three

Compounds and phosphonium oxide compounds.

O- oxime compounds, including N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzyloxy- 1-(4-phenylsulfanylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-ring Pentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylhydrothiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylhydrothiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl -6-(2-Methylbenzyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2 -Methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzyl)-9H-carbazol-3-yl)ethane-1- Imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1- Imine and N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1 -Keto-2-imine, etc. In addition, as the O-acetoxime compound, commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF Co., Ltd.), and N-1919 (manufactured by ADEKA Co., Ltd.), etc. can also be used. Among them, the O-acyl oxime compound is selected from N-benzyloxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzyl Acetyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylhydrothiophenyl) At least one of the group formed by -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzyloxy-1-(4-phenylhydrothiophenyl) ) Octan-1-one-2-imine is more preferred.

For alkylphenone compounds, 2-methyl-2-morpholinyl-1-(4- Methyl sulfanyl phenyl) propane-1-one, 2-dimethylamino-1-(4-morpholinyl phenyl)-2-benzylbutane-1-one and 2-(di Methylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. As the alkylphenone compound, commercially available products such as Irgacure 369, 907, and 379 (all of the above are manufactured by BASF Co., Ltd.) can also be used.

For alkylphenone compounds, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy Yl)phenyl)propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomer, α,α-diethoxy acetophenone and benzyl dimethyl acetal.

Biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis( 2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.) And 4,4',5,5'-position phenyl group is substituted with carbonyl alkoxy imidazole compound (refer to Japanese Patent Application Laid-Open No. 7-10913 etc.) etc.

化合物而言，可列舉2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-胡椒基(piperonyl)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5- 三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三

及2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 three

For the compound, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

Wait.

As the phosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide and the like can be mentioned.

The polymerization initiator (D) may further include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone, methyl o-benzoyl benzoate, 4 -Phenylbenzophenone, 4-Benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'tetra(tert-butylperoxycarbonyl)benzophenone and Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridine Ketones, benzyl, methyl phenylglyoxylate and titanocene compounds, etc.

These compounds are preferably used in combination with the polymerization initiator (D1) (particularly amines) described later.

化合物、醯基膦氧化物化合物、O-醯基肟化合物及聯咪唑化合物所形成之群組中的至少一種聚合起始劑為佳，以含有O-醯基肟化合物的聚合起始劑更佳。 The polymerization initiator (D) contains a compound selected from alkylphenone compounds, three

At least one polymerization initiator selected from the group consisting of the compound, the phosphine oxide compound, the O-oxime compound, and the biimidazole compound is preferred, and the polymerization initiator containing the O-oxime compound is more preferred .

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, and more preferably 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

In the total amount of solid content in the colored curable resin composition, polymerization The content of the starting agent (D) is preferably 0.001 to 40 parts by mass, and more preferably 0.01 to 30 parts by mass.

<Polymerization initiation aid (D1)>

The polymerization start auxiliary agent (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. When the polymerization initiator (D1) is contained, it can usually be used in combination with the polymerization initiator (D).

The polymerization initiation auxiliary (D1) includes amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

For amine compounds, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as Michler's Ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(ethyl (Methylamino)benzophenone, etc., preferably 4,4'-bis(diethylamino)benzophenone. In addition, commercial products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can also be used as the amine compound.

As for the alkoxyanthracene compound, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

The thioxanthone compound includes 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1- Chloro-4-propoxythioxanthone and so on.

For the carboxylic acid compound, phenyl thio acetic acid, methyl phenyl thio acetic acid, ethyl phenyl thio acetic acid, methyl ethyl phenyl thio acetic acid, dimethyl phenyl hydrogen Thioacetic acid, methoxyphenyl sulfanyl acetic acid, dimethoxyphenyl sulfanyl acetic acid, chlorophenyl sulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid, etc.

When using these polymerization initiators (D1), the content of the total solid content in the colored curable resin composition is preferably 0.001 to 30% by mass, and more preferably 0.01 to 20% by mass. good.

When using these polymerization initiation aids (D1), relative to 100 parts by mass of the total amount of resin (B) and polymerizable compound (C), the content is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass Better servings.

<Solvent (E)>

As for the solvent (E), the same solvents as those exemplified in the aforementioned coloring composition can be mentioned.

The content of the solvent (E) relative to the total amount of the colored curable resin composition is preferably 70 to 95% by mass, more preferably 75 to 90% by mass.

<Leveling Agent (F)>

As the leveling agent (F), a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom, etc. can be cited. These leveling agents may have a polymerizable group on the side chain.

Polysiloxane-based surfactants include surfactants having siloxane bonds in the molecule, and the like. Specifically, Toray Silicone's DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray Dowcorning (stock)), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

The fluorine-based surfactant includes a surfactant having a fluorocarbon chain in the molecule, and the like. Specifically, Fluorad (registered trademark) FC430, FC431 (Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718- K (DIC (stock) system), F-Top (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass (Stock) system) and E5844 (made by Daikin Fine Chemicals Research Institute), etc.

Examples of the silicone-based surfactants having fluorine atoms include those having silicone bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (DIC (stock) system), etc. can be cited.

When the leveling agent (F) is contained, relative to the total amount of the colored composition or colored curable resin composition, its content is usually 0.0005 mass% to 1 mass %, preferably 0.001 mass% to 0.5 mass %, and It is more preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and still more preferably 0.005% by mass or more and 0.1% by mass or less. When the content of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be improved.

<Antioxidant>

In terms of improving the heat resistance and light resistance of the colorant, it is better to use the antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used in industry, and phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like can be used.

-2,4,6(1H,3H,5H)-三酮，BASF(股)製)、Irganox 3790(Irganox 3790：1,3,5-參(3,5(4-第三丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三

-2,4,6(1H,3H,5H)-三酮，BASF(股)製)、Irganox 1035(Irganox 1035：硫代二乙烯雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]，BASF(股)製)、Irganox 1135(Irganox 1135：苯丙酸、3,5-雙(1,1-二甲基乙基)-4-羥基、C7至C9側鏈烷醚，BASF(股)製)、Irganox 1520L(Irganox 1520L：4,6-雙(辛基硫代甲基)-鄰-甲酚，BASF(股)製)、Irganox 3125(BASF(股)製)、Irganox 565(Irganox 565：2,4-雙(正辛基硫代)-6-(4-羥基3’,5’-二-第三丁基苯胺基)-1,3,5-三

，BASF(股)製)、Adekastab AO-80(Adekastab AO-80：3,9-雙(2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧 基)-1,1-二甲基乙基)-2,4,8,10-四氧雜螺旋(5,5)十一烷，(股)ADEKA製)、Sumilizer BHT(住友化學(股)製)、Sumilizer GA-80(住友化學(股)製)、Sumilizer GS(住友化學(股)製)、Cyanox 1790((股)Cytech製)及維生素E(Eisai(股)製)等。 The aforementioned phenolic antioxidants include, for example, Irganox 1010 (Irganox 1010: neopentylerythritol four [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF (stocks) )), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF (Stock)), Irganox 1330 (Irganox 1330 ：3,3',3”,5,5',5”-hexa-tertiary butyl-a,a',a”-(methylene-2,4,6-triyl) three-pair- Cresol, manufactured by BASF (Stock)), Irganox 3114 (Irganox 3114: 1,3,5-gin (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-Triketone, manufactured by BASF (Stock)), Irganox 3790 (Irganox 3790: 1,3,5-reference -Hydroxy-2,6-xylyl)methyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-triketone, manufactured by BASF (Stock), Irganox 1035 (Irganox 1035: thiodiethylenebis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate], manufactured by BASF (Stocks), Irganox 1135 (Irganox 1135: phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7 To C9 side chain alkyl ether, manufactured by BASF (stock), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF (stock)), Irganox 3125 (BASF) (Stock) system), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy 3',5'-di-tertiary butylanilino)-1,3 ,5-three

, BASF (Stock) system), Adekastab AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propane Oxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiral (5,5) undecane, (made by ADEKA), Sumilizer BHT (Sumitomo Chemical (Stock) )), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytech (Stock) and Vitamin E (manufactured by Eisai Co., Ltd.)

The aforementioned phosphorus antioxidants include, for example, Irgafos 168 (Irgafos 168: ginseng (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), Irgafos 12 (Irgafos 12: Parameter [2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxphosphin-6-yl]oxy]ethyl] Amine, made by BASF (stock), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) ethyl phosphite, BASF (stock)) System), Adekastab 329K (Adeka (shares) system), Adekastab PEP36 (Adeka (shares) system), Adekastab PEP-8 (Adeka (shares) system), Sandstab P-EQP (Clariant company system), Weston 618 (GE company Manufactured by GE), Weston 619G (manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer GP (Sumilizer GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propane Oxy]-2,4,8,10-tetra-tert-butyl-butyldibenzo[d,f][1.3.2]dioxaphosphepin) (Sumitomo Chemical Co., Ltd.)制) etc.

The sulfur-based antioxidants include, for example, dilauryl thiodipropionate, dimyristyl or distearyl and other dialkylthiodipropionate compounds, and tetrakis[methylene (3-dodecane) Alkylthio)propionate] β-alkyl mercaptan propionate compounds of polyhydric alcohols such as methane.

<Other ingredients>

The colored composition and colored curable resin composition of the present invention may also contain fillers, other polymer compounds, adhesion promoters, Antioxidants, light stabilizers, chain transfer agents, and other additives known in this technical field.

As for the adhesion promoter, for example, vinyl trimethoxysilane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidoxy propyl trimethoxy silane 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl) Ethyl trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-thiol group Propyl trimethoxysilane, 3-hydrothiopropyl trimethoxysilane, 3-isocyanatomethyl propyl triethoxysilane, N-2-(aminoethyl)-3-amino group Propylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-amino Propyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyl diethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane and N-phenyl-3-aminopropyl triethoxysilane, etc.

<Color filter>

A color filter can be formed from the colored curable resin composition of the present invention. The method of forming a colored pattern includes a photolithograph method, an inkjet method, and a printing method. Among them, photolithography is preferred. Photolithography is a method of applying the colored curable resin composition on a substrate, drying it to form a colored curable resin composition layer, and exposing the colored curable resin composition through a photomask to develop images. In photolithography, the above-mentioned colored curable resin can be formed by not using a photomask and/or not performing development during exposure. The color coating film of the hardened material of the composition. The colored pattern or colored coating film thus formed is the color filter of the present invention.

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

As for the substrate, a glass plate, a resin plate, polysiloxane, or a thin film of aluminum, silver, silver/copper/palladium alloy, etc. formed on the aforementioned substrate can be used. On these substrates, additional color filter layers, resin layers, transistors, and circuits can also be formed.

The formation of pixels of each color by photolithography can be performed with known or commonly used equipment and conditions. For example, it can be produced as follows.

First, the colored curable resin composition is coated on the substrate, and volatile components such as the solvent are removed by heating and drying (pre-baking) and/or under reduced pressure and dried to obtain a smooth colored curable resin composition layer .

The coating method includes a spin coating method, a slit coating method, and a slit and spin coating method.

Next, the colored curable resin composition layer is exposed through a photomask for forming the intended colored pattern. It is preferable to irradiate parallel light uniformly on the entire exposure surface, or to perform precise positioning between the mask and the substrate on which the colored curable resin composition layer has been formed, a projection lithography machine (mask aligner) and a stepper are used (Stepper) and other exposure devices.

By contacting the exposed colored hardened resin composition layer with a developing solution for development, a colored pattern can be formed on the substrate. Through development, the unexposed part of the colored curable resin composition layer can be dissolved in the developer Remove.

The developing solution is preferably an aqueous solution of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide.

The imaging method may be any of a paddle method, a dipping method, and a spray method. In addition, the substrate can be tilted to any angle during development.

The developed substrate should preferably be washed with water.

In addition, it is better to perform post bake on the obtained coloring pattern.

The aforementioned color filters can be used as color filters used in display devices (such as liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices, and can be used as color filters used in liquid crystal displays Light film.

[Example]

Hereinafter, examples are given to explain the present invention more specifically, but the present invention is not limited to the scope of the following examples.

In the following synthesis examples and examples, the structure of the compound was determined by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) or mass analysis (LC; Agilent 1200 type, MASS; Agilent LC/MSD6130 type) confirm.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene was performed by the GPC method under the following conditions.

Device: HLC-8120GPC (Tosoh (stock) system)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: Tetrahydrofuran

Flow rate: 1.0mL/min

Analysis of the solid content of the sample: 0.001 to 0.01% by mass

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE (standard polystyrene) F-40, F-4, F-288, A-2500, A-500 (Tosoh (stock) system)

The polystyrene-converted weight average molecular weight (Mw) and the ratio (Mw/Mm) of the number average molecular weight (Mm) obtained in the above were used as the degree of dispersion.

Example 1

11.0 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 91.5 parts of methanol were mixed. While keeping the temperature of the obtained mixture at 2°C, a mixture of 8.59 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 77.6 parts of methanol was dropped over 1 hour and 45 minutes at 2°C Stir for 6 hours and 40 minutes. To the obtained mixture, 4.18 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 2°C for 1 hour and 45 minutes. While keeping the temperature of the obtained mixture below 4°C, 17.0 parts of acetic acid was added. 23.9 parts of neopentylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was stirred at room temperature for 87 hours. 10.8 parts of neopentylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.40 parts of acetic acid were added to the obtained mixture, and the mixture was stirred at 40°C for 4 hours and 30 minutes. The obtained mixture was filtered, and the residue was washed with 360 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain a compound represented by formula (I-1) 22.8 copies.

<Identification of the compound represented by formula (I-1)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 362

Accurate quality: 361

Example 2

2.59 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.1 parts of methanol were mixed. While keeping the temperature of the obtained mixture at 2°C, a mixture of 1.50 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 23.2 parts of methanol was dropped in this mixture over 1 hour and 10 minutes. Stir at 2°C for 2 hours and 20 minutes. While keeping the temperature of the obtained mixture below 3°C, 2.35 parts of acetic acid was added, and 4.13 parts of neopentylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The obtained mixture was stirred at room temperature for 3 hours and 35 minutes and at 40°C for 1 hour and 45 minutes. 4.16 parts of neopentylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was stirred at 40°C for 1 hour and 30 minutes. The obtained mixture was stirred at room temperature for 37 hours. To the obtained mixture, 1.89 parts of neopentylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.24 parts of acetic acid were added, and the mixture was stirred at 40°C for 5 hours and 15 minutes. The obtained mixture was filtered, and the residue was washed with 198 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain 5.58 parts of a compound represented by formula (I-2).

<Identification represented by formula (I-2)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 407

Accurate quality: 406

Example 3

7.02 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 61.6 parts of methanol were mixed. While keeping the temperature of the obtained mixture at 2°C, a mixture of 8.20 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 74.6 parts of methanol was dropped over 1 hour and 30 minutes. The obtained mixture was stirred at 2°C for 6 hours and 15 minutes. While keeping the temperature of the obtained mixture below 4°C, 10.7 parts of acetic acid was added. 17.6 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was stirred at room temperature for 44 hours. The obtained mixture was filtered, and the residue was washed with 800 parts of methanol. The obtained residue was dried under reduced pressure at 60°C to obtain 18.0 parts of a compound represented by formula (I-3).

<Identification of the compound represented by formula (I-3)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 402

Accurate quality: 401

Example 4

4.12 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 37.2 parts of methanol were mixed. While keeping the temperature of this mixture at 2°C, a mixture of 4.82 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 45.2 parts of methanol was dropped over 1 hour in this mixture. The obtained mixture was stirred at 2°C for 6 hours. While keeping the temperature of the obtained mixture below 4°C, 6.29 parts of acetic acid was added. 12.7 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was stirred at 2°C for 1 hour and at room temperature for 20 minutes. The obtained mixture was stirred at 40°C for 2 hours, at room temperature for 11 hours, and at 40°C for 5 hours and 40 minutes. 3.18 parts of acetic acid and 6.45 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. The obtained mixture was stirred at 40°C for 4 hours and at room temperature for 62 hours. The obtained mixture was filtered and washed three times with the same volume of methanol as the residue. The obtained residue was recrystallized with N,N-dimethylformamide. The obtained residue was dried under reduced pressure at 60°C to obtain 9.99 parts of a compound represented by formula (I-4).

<Identification of the compound represented by formula (I-4)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Accurate quality: 469

Example 5

4.07 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 36.0 parts of methanol were mixed. While keeping the temperature of the obtained mixture at 2°C, a mixture of 4.76 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 44.3 parts of methanol was dropped over 1 hour and 10 minutes. The obtained mixture was stirred at 2°C for 5 hours and 25 minutes. While keeping the temperature of the obtained mixture below 3°C, 6.23 parts of acetic acid was added. 12.6 parts of 4-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was stirred at 40°C for 40 minutes. 456 parts of methanol was added to the obtained mixture, and the mixture was stirred at 40°C for 3 hours and at room temperature for 37 hours. 3.14 parts of acetic acid, 6.31 parts of 4-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 124 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 6 hours and 40 minutes. The obtained mixture was stirred at room temperature for 18 hours. The obtained mixture was filtered, and the residue was washed with 554 parts of methanol. 1,740 parts of N,N-dimethylformamide was added to the obtained residue, and after stirring at 80 degreeC, it filtered while keeping it at 80 degreeC. Obtain the residue and filtrate (ROE-1). The obtained residue was washed with 150 parts of N,N-dimethylformamide. Obtain the residue and lotion (SEN-1). The obtained residue was dried under reduced pressure at 60°C to obtain 4.88 parts of a compound represented by formula (I-5). The obtained filtrate (ROE-1) was combined with the washing liquid (SEN-1), and it was allowed to stand at room temperature for 12 hours. The obtained mixture was filtered, and the residue was washed 3 times with the same volume of N,N-dimethylformamide as the residue. The obtained residue was dried under reduced pressure at 60°C to obtain 5.16 parts of a compound represented by formula (I-5).

<Identification of the compound represented by formula (I-5)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Accurate quality: 469

Example 6

10.0 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 93 parts of methanol were mixed. While keeping the temperature at 2°C, a mixture of 11.7 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 110 parts of methanol was dropped in the obtained mixture over 1 hour and 15 minutes. The obtained mixture was stirred at 5°C for 3 hours. While maintaining the temperature below 5°C, 7.71 parts of acetic acid and 8 parts of methanol were added to the obtained mixture. 11.4 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture. After the obtained mixture was stirred at 2°C for 40 minutes, it was stirred at room temperature for 17 hours and 40 minutes. 109 parts of methanol was added to the obtained mixture, and stirred at room temperature for 1 hour and 20 minutes. 6.41 parts of acetic acid, 10.1 parts of barbituric acid, and 16.0 parts of methanol were added to the obtained mixture. After the obtained mixture was stirred at room temperature for 5 hours, it was stirred at 40°C for 2 hours. 344 parts of water was added to the obtained mixture. After the obtained mixture was stirred at 40°C for 3 hours and 25 minutes, it was stirred at room temperature for 16 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 1.55 parts of the compound represented by formula (I-6).

<Identification of the compound represented by formula (I-6)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 385

Accurate quality: 384

Example 7

5.00 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 42.0 parts of methanol were mixed. While maintaining at 2° C., a mixture of 5.83 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 52.5 parts of methanol was dropped in the obtained mixture over 1 hour and 30 minutes. The obtained mixture was stirred at 2°C for 6 hours. While keeping the temperature below 4°C, 7.59 parts of acetic acid were added to the obtained mixture, and 17.4 parts of methyl 4-cyanoacetoxybenzoate (synthesized according to the method described in Japanese Patent Laid-Open No. 8-176154) and 17.4 parts 682 parts of methanol. After the obtained mixture was stirred at room temperature for 4 hours, it was stirred at 40°C for 48 hours. After distilling the solvent off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 2.21 parts of the compound represented by formula (I-7).

<Identification of the compound represented by formula (I-7)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 518

Accurate quality: 517

Example 8

8.10 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 69.0 parts of methanol were mixed. While maintaining the temperature at 2° C., a mixture of 4.68 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 45.0 parts of methanol was dropped into the obtained mixture over 50 minutes. The obtained mixture was stirred at 2°C for 2 hours and 30 minutes. While keeping the temperature at 2°C, 7.35 parts of acetic acid and 18.7 parts of phenylsulfonylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. After the obtained mixture was stirred at room temperature for 15 hours, it was stirred at 40°C for 50 hours. The obtained mixture was divided into two halves, and mixture 1 and mixture 2 were obtained.

After distilling off the solvent of the mixture 1 with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.0273 parts of the compound represented by formula (I-8).

2.00 parts of acetic acid, 3.02 parts of barbituric acid, 50 parts of methanol, and 102 parts of water were added to the mixture 2, and the mixture was stirred at 40°C for 12 hours. After removing the solvent from the obtained mixture using a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.0313 parts of the compound represented by formula (I-9).

<Identification of the compound represented by formula (I-8)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 519

Accurate quality: 518

<Identification of the compound represented by formula (I-9)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 466

Accurate quality: 465

Example 9

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-chlorobenzylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was performed in the same manner as in Example 7. , The compound represented by formula (I-10) is obtained.

<Identification of the compound represented by formula (I-10)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Accurate quality: 469

Example 10

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to methyl 3-cyanoacetoxybenzoate, the rest was performed in the same manner as in Example 7 to obtain the formula (I- 11) The compound represented.

<Identification of the compound represented by formula (I-11)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 518

Accurate quality: 517

Synthesis example 1

Except for maintaining its molar ratio, while adding 4-cyanoacetoxybenzoic acid Except that the methyl ester was changed to phenylsulfonylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), the rest was performed in the same manner as in Example 7 to obtain the compound represented by formula (I-12).

<Identification of the compound represented by formula (I-12)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 474

Accurate quality: 473

Example 11

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-methylbenzylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was the same as in Example 7. By operation, the compound represented by formula (I-13) was obtained.

<Identification of the compound represented by formula (I-13)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 430

Exact quality: 429

Example 12

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-methylbenzylacetonitrile (manufactured by Sigma Aldrich, Japan), the rest was the same as Example 7 Operation to obtain the formula (I-14) Compound.

<Identification of the compound represented by formula (I-14)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 430

Exact quality: 429

Example 13

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-methylbenzylacetonitrile (manufactured by Sigma Aldrich, Japan), the rest was the same as in Example 7 Operation to obtain the compound represented by formula (I-15).

<Identification of the compound represented by formula (I-15)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 430

Exact quality: 429

Example 14

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-nitrobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-16) Represents the compound.

<Identification of the compound represented by formula (I-16)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 492

Accurate quality: 491

Example 15

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-nitrobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-17) Represents the compound.

<Identification of the compound represented by formula (I-17)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 492

Accurate quality: 491

Example 16

Except that while keeping its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-nitrobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-18) Represents the compound.

<Identification of the compound represented by formula (I-18)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 492

Accurate quality: 491

Example 17

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-cyanobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-19) Represents the compound.

<Identification of the compound represented by formula (I-19)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 452

Accurate quality: 451

Example 18

Except that methyl 4-cyanoacetoxybenzoate was changed to 3-dimethylaminobenzylacetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Example 7 to obtain the formula (I -20) The compound represented.

<Identification of the compound represented by formula (I-20)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 488

Accurate quality: 487

Example 19

Except for maintaining its molar ratio, while adding 4-cyanoacetoxybenzoic acid Except that the methyl ester was changed to 1-naphthoacetonitrile, the remaining operations were the same as in Example 7 to obtain the compound represented by formula (I-21).

<Identification of the compound represented by formula (I-21)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 502

Accurate quality: 501

Example 20

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-naphthoacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-22) Compound.

<Identification of the compound represented by formula (I-22)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 502

Accurate quality: 501

Example 21

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-trifluoromethylbenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I- 23) The compound represented.

<Identification of the compound represented by formula (I-23)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 538

Accurate quality: 537

Example 22

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-trifluoromethylbenzylacetonitrile (manufactured by Sigma Aldrich, Japan), the rest was the same as in Example 7. In the same manner, the compound represented by formula (I-24) was obtained.

<Identification of the compound represented by formula (I-24)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 538

Accurate quality: 537

Example 23

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-trifluoromethylbenzylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was the same as in Example 7. In the same manner, the compound represented by formula (I-25) was obtained.

<Identification of the compound represented by formula (I-25)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 538

Accurate quality: 537

Example 24

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-fluorobenzylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was performed in the same manner as in Example 7. , The compound represented by formula (I-26) is obtained.

<Identification of the compound represented by formula (I-26)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 438

Accurate quality: 437

Example 25

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-fluorobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-27) expression compound of.

<Identification of the compound represented by formula (I-27)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 438

Accurate quality: 437

Example 26

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-fluorobenzylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was performed in the same manner as in Example 7. , The compound represented by formula (I-28) is obtained.

<Identification of the compound represented by formula (I-28)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 438

Accurate quality: 437

Example 27

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-bromobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-29) expression compound of.

<Identification of the compound represented by formula (I-29)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 558

Accurate quality: 557

Example 28

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-bromobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-30) expression compound of.

<Identification of the compound represented by formula (I-30)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 558

Accurate quality: 557

Example 29

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-bromobenzylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was performed in the same manner as in Example 7. , The compound represented by formula (I-31) is obtained.

<Identification of the compound represented by formula (I-31)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 558

Accurate quality: 557

Example 30

Except for maintaining its molar ratio, while adding 4-cyanoacetoxybenzoic acid Except that the methyl ester was changed to 2-methoxybenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the compound represented by formula (I-32).

<Identification of the compound represented by formula (I-32)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 462

Accurate quality: 461

Example 31

Except that methyl 4-cyanoacetoxybenzoate was changed to 3-methoxybenzylacetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Example 7 to obtain the formula (I-33 ) Represents the compound.

<Identification of the compound represented by formula (I-33)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 462

Accurate quality: 461

Example 32

The same as Example 7 except that methyl 4-cyanoacetoxybenzoate was changed to 4-methoxybenzylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.) while maintaining its molar ratio. To obtain the compound represented by formula (I-34).

<Identification of the compound represented by formula (I-34)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 462

Accurate quality: 461

Example 33

13.8 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 115 parts of methanol were mixed. While keeping it at 2 to 3°C, a mixture of 7.94 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 74.0 parts of methanol was dropped over 40 minutes in the obtained mixture. The obtained mixture was stirred at 2 to 3°C for 4 hours. While keeping the obtained mixture below 3°C, 12.5 parts of acetic acid was added, and 25.4 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 parts of methanol were added. After the obtained mixture was stirred at room temperature for 18 hours, it was stirred at 43°C for 5 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 1.02 parts of the compound represented by formula (I-35).

<Identification of the compound represented by formula (I-35)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 447

Accurate quality: 446

Example 34

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3,4-dichlorobenzylacetonitrile (manufactured by Sigma Aldrich, Japan), the rest was the same as in Example 7. In the same manner, the compound represented by formula (I-36) was obtained.

<Identification of the compound represented by formula (I-36)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 538

Accurate quality: 537

Example 35

In addition to maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to (5,6,7,8-tetrahydro-2-naphthomethyl)acetonitrile (Sigma Aldrich Co., Ltd., Japan) Except for manufacturing), the rest was the same as in Example 7 to obtain the compound represented by formula (I-37).

<Identification of the compound represented by formula (I-37)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 510

Accurate quality: 509

Example 36

Except for maintaining its molar ratio, while adding 4-cyanoacetoxybenzoic acid Except that the methyl ester was changed to 4-dimethylaminobenzylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was carried out in the same manner as in Example 7 to obtain the compound represented by formula (I-38).

<Identification of the compound represented by formula (I-38)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 488

Accurate quality: 487

Synthesis Example 2

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to methylsulfonylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was performed in the same manner as in Example 7 to obtain The compound represented by formula (I-39).

<Identification of the compound represented by formula (I-39)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 350

Accurate quality: 349

Synthesis Example 3

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to (4-bromophenylsulfonyl)acetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the rest was the same as in Example 7. Do the same to obtain the formula (I-40) compound of.

<Identification of the compound represented by formula (I-40)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 630

Exact quality: 629

Example 37

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to methyl 2-cyanoacetoxybenzoate, the rest was performed in the same manner as in Example 7 to obtain the formula (I- 41) The compound represented.

<Identification of the compound represented by formula (I-41)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 518

Accurate quality: 517

Example 38

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-sulfamoylbenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I- 42) The compound represented.

Example 39

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-cyanoacetoxybenzoic acid, the rest was performed in the same manner as in Example 7 to obtain the formula (I-43) Represents the compound.

<Identification of the compound represented by formula (I-43)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Accurate quality: 489

Example 40

Except that methyl 4-cyanoacetoxybenzoate was changed to 3-cyanoacetoxybenzoic acid while maintaining its molar ratio, the rest was performed in the same manner as in Example 7 to obtain the formula (I-44) Represents the compound.

<Identification of the compound represented by formula (I-44)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Accurate quality: 489

Example 41

Except that methyl 4-cyanoacetoxybenzoate was changed to 4-cyanoacetoxybenzoic acid while maintaining its molar ratio, the rest was performed in the same manner as in Example 7 to obtain the formula (I-45) Represents the compound.

<Identification of the compound represented by formula (I-45)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Accurate quality: 489

Example 42

Except that methyl 4-cyanoacetoxybenzoate was changed to 3-cyanoacetoxybenzoic acid while maintaining its molar ratio, the rest was performed in the same manner as in Example 7 to obtain the formula (I-46) Represents the compound.

Example 43

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-hydroxybenzoylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-47) expression compound of.

<Identification of the compound represented by formula (I-47)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 434

Accurate quality: 433

Example 44

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-hydroxybenzoylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-48) expression compound of.

<Identification of the compound represented by formula (I-48)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 434

Accurate quality: 433

Example 45

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-hydroxybenzoylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-49) expression compound of.

<Identification of the compound represented by formula (I-49)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 434

Accurate quality: 433

Example 46

Except that methyl 4-cyanoacetoxybenzoate was changed to 2-aminobenzylacetonitrile while maintaining its molar ratio, the rest was performed in the same manner as in Example 7 to obtain the formula (I-50) Represents the compound.

Example 47

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-aminobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-51) Represents the compound.

Example 48

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-aminobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-52) Represents the compound.

Example 49

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-acetoxybenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-53 ) Represents the compound.

<Identification of the compound represented by formula (I-53)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 486

Accurate quality: 485

Example 50

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-diethylaminobenzylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I -54) The compound represented by.

Example 51

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 4-methylthiobenzoylacetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I- 55) The compound represented.

Synthesis Example 4

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to (4-acetamidophenylsulfonyl)acetonitrile, the rest was performed in the same manner as in Example 7 to obtain A compound represented by formula (I-56).

Example 52

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to (2-pyridylsulfonyl)acetonitrile, the rest was performed in the same manner as in Example 7 to obtain the formula (I-57 ) Represents the compound.

Example 53

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to N-octyl-((4-cyanoacetoxy)phenyl)sulfonamide, the rest is the same as in the examples 7 In the same manner, the compound represented by formula (I-58) was obtained.

Example 54

Except that methyl 4-cyanoacetoxybenzoate was changed to N,N-dibutyl-((4-cyanoacetoxy)phenyl)sulfonamide while maintaining its molar ratio, the rest In the same manner as in Example 7, the compound represented by formula (I-59) was obtained.

Example 55

Except for changing methyl 4-cyanoacetoxybenzoate to N,N-diphenyl Except for -((4-cyanoacetoxy)phenyl)sulfonamide, the rest was carried out in the same manner as in Example 7 to obtain a compound represented by formula (I-60).

Example 56

While stirring 7.6 parts of fuming sulfuric acid (25%) (manufactured by Wako Pure Chemical Industries, Ltd.) at 3°C, 0.513 parts of the compound represented by the formula (I-3) obtained in Example 3 was added. 3.8 parts of oleum (25%) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained mixture. While stirring the obtained mixture, it took 3 hours and 30 minutes to raise to 15°C. 139 parts of ice water was added to the obtained mixture, and 38.2 parts of sodium chloride was added. The obtained mixture was filtered, and the obtained residue was washed with 64 parts of 21.5% sodium chloride aqueous solution. The obtained residue was dried under reduced pressure at 60°C to obtain 1.02 parts of the compound represented by formula (I-61).

<Identification of the compound represented by formula (I-61)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 560

Accurate quality: 561

Example 57

12.2 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 103 parts of methanol were mixed. While keeping it at 4 to 6°C, 28% in the obtained mixture A mixture of 14.3 parts of sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 130 parts of methanol was dropped over 2 hours and 10 minutes. The obtained mixture was stirred at 4 to 6°C for 6 hours. While keeping the temperature at 5°C or lower, 9.37 parts of acetic acid and 13.8 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. The obtained mixture was stirred for 15 hours at room temperature. To the obtained mixture, 1.00 part of acetic acid and 1.39 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at room temperature for 3 hours and at 40°C for 2 hours and 30 minutes. 1.44 parts of acetic acid and 2.13 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture, and the mixture was stirred at 40°C for 3 hours. 0.985 parts of acetic acid, 1.46 parts of benzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 170 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 2 hours. To the obtained mixture, 9.29 parts of acetic acid, 12.2 parts of barbituric acid, and 17 parts of methanol were added, and the mixture was stirred at 40°C for 20 hours. 9.29 parts of acetic acid, 14.4 parts of barbituric acid, and 14 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 18 hours. The obtained mixture was filtered. The obtained residue was washed twice with a mixture of 200 parts of water and 200 parts of methanol, once with a mixture of 219 parts of water and 219 parts of methanol, and once with 500 parts of water. The obtained residue was dried under reduced pressure at 60°C to obtain 31.3 parts of a mixture containing the compound represented by formula (I-3) and the compound represented by formula (I-6).

<Identification of the compound represented by formula (I-3)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 402

Accurate quality: 401

<Identification of the compound represented by formula (I-6)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 385

Accurate quality: 384

Example 58

11.5 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 136 parts of methanol were mixed. While keeping it at 2 to 4°C, a mixture of 13.5 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 101 parts of methanol was dropped over 1 hour in the obtained mixture. While keeping the obtained mixture at 5°C or lower, it was stirred for 6 hours. While maintaining at 4 to 8°C, 8.88 parts of acetic acid, 3.2 parts of methanol, and 16.3 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. The obtained mixture was stirred at room temperature for 16 hours. 1.02 parts of acetic acid, 1.64 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts of methanol were added to the obtained mixture, and the mixture was stirred at room temperature for 1.5 hours and at 40°C for 6 hours. 1.35 parts of acetic acid, 2.44 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 3 hours. To the obtained mixture, 1.16 parts of acetic acid, 2.03 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts of methanol were added, and the mixture was stirred at 40°C for 17 hours. 8.83 parts of acetic acid, 12.6 parts of barbituric acid, and 14 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40°C for 22 hours. To the obtained mixture, 4.40 parts of acetic acid, 5.75 parts of barbituric acid, and 14 parts of methanol were added, and the mixture was stirred at 40°C for 9 hours and at room temperature for 4 hours. Will get The resulting mixture was filtered. The obtained residue was washed once with 393 parts of methanol, and once with a mixture of 393 parts of water and 393 parts of methanol. 800 parts of methanol was added to the obtained residue, and it stirred at 40 degreeC for 2 hours. The obtained mixture was filtered. The obtained residue was dried under reduced pressure at 40°C to obtain 40.7 parts of a mixture containing the compound represented by formula (I-4) and the compound represented by formula (I-63).

<Identification of the compound represented by formula (I-4)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Accurate quality: 469

<Identification of the compound represented by formula (I-63)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 419

Accurate quality: 418

Example 59

Except that while maintaining its molar ratio, the 2-chlorobenzylacetonitrile was changed to 4-chlorobenzylacetonitrile, the same procedure as in Example 58 was carried out to obtain a compound containing formula (I-5) and A mixture of compounds represented by formula (I-64).

<Identification of the compound represented by formula (I-5)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Accurate quality: 469

<Identification of the compound represented by formula (I-64)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 419

Accurate quality: 418

Example 60

Except that while maintaining its molar ratio, 2-chlorobenzylacetonitrile was changed to neopentylacetonitrile, the same procedure as in Example 58 was carried out to obtain a compound represented by formula (I-1) and formula (I -65) A mixture of the compounds represented.

<Identification of the compound represented by formula (I-1)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 362

Accurate quality: 361

<Identification of the compound represented by formula (I-65)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 365

Accurate quality: 364

Example 61

Except that the phthalonitrile was changed to 4-nitrophthalonitrile while maintaining its molar ratio, the same operation as in Example 58 was carried out to obtain a compound represented by formula (I-66) and a compound represented by formula (I-67) A mixture of compounds.

<Identification of the compound represented by formula (I-66)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 515

Accurate quality: 514

<Identification of the compound represented by formula (I-67)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 464

Accurate quality: 463

Example 62

Except for changing phthalonitrile to 4-nitrophthalonitrile while maintaining its molar ratio, and changing 2-chlorobenzylacetonitrile to 4-chlorobenzylacetonitrile while maintaining its molar ratio, In the same manner as in Example 58, a mixture containing the compound represented by formula (I-68) and the compound represented by formula (I-69) was obtained.

<Identification of the compound represented by formula (I-68)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 515

Accurate quality: 514

<Identification of the compound represented by formula (I-69)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 464

Accurate quality: 463

Example 63

In addition to maintaining its molar ratio, while changing the phthalonitrile to 4-nitrophthalonitrile, while maintaining its molar ratio, the 2-chlorobenzylacetonitrile was changed to Except for the neopentylacetonitrile, the same procedure as in Example 58 was performed to obtain a mixture containing the compound represented by formula (I-2) and the compound represented by formula (I-70).

<Identification of the compound represented by formula (I-2)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 407

Accurate quality: 406

<Identification of the compound represented by formula (I-70)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 410

Accurate quality: 409

Example 64

Except that while maintaining its molar ratio, phthalonitrile was changed to 4-nitrophthalonitrile, while maintaining its molar ratio, 2-chlorobenzylacetonitrile was changed to benzylacetonitrile, the same as in the examples 58 In the same manner, a mixture containing the compound represented by formula (I-35) and the compound represented by formula (I-72) is obtained.

<Identification of the compound represented by formula (I-35)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 447

Accurate quality: 446

<Identification of the compound represented by formula (I-72)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 430

Exact quality: 429

Example 65

Except for changing the barbituric acid to benzylacetonitrile while maintaining its molar ratio, the same procedure as in Example 58 was carried out to obtain a compound represented by formula (I-4) and represented by formula (I-73) A mixture of compounds.

<Identification of the compound represented by formula (I-4)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Accurate quality: 469

<Identification of the compound represented by formula (I-73)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 436

Accurate quality: 435

Example 66

Except that while maintaining its molar ratio, 2-chlorobenzylacetonitrile was changed to 4-chloroacetonitrile, and barbituric acid was changed to benzylacetonitrile, the same procedure as in Example 58 was carried out to obtain the formula containing A mixture of the compound represented by (I-5) and the compound represented by formula (I-74).

<Identification of the compound represented by formula (I-5)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Accurate quality: 469

<Identification of the compound represented by formula (I-74)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 436

Accurate quality: 435

Example 67

Except that while maintaining its molar ratio, phthalonitrile was changed to 4-nitrophthalonitrile, and while maintaining its molar ratio, barbituric acid was changed to benzylacetonitrile, the same procedure as in Example 58 was performed. To obtain a mixture containing the compound represented by formula (I-66) and the compound represented by formula (I-75).

<Identification of the compound represented by formula (I-66)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 515

Accurate quality: 514

<Identification of the compound represented by formula (I-75)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 481

Accurate quality: 480

Example 68

In addition to maintaining its molar ratio, while changing the phthalonitrile to 4-nitrophthalonitrile, while maintaining its molar ratio, the 2-chlorobenzylacetonitrile was changed to 4-Chlorobenzylacetonitrile, except that the barbituric acid was changed to benzylacetonitrile, the same procedure as in Example 58 was carried out to obtain a compound represented by formula (I-68) and represented by formula (I-76) A mixture of compounds.

<Identification of the compound represented by formula (I-68)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 515

Accurate quality: 514

<Identification of the compound represented by formula (I-9)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 481

Accurate quality: 480

Example 69

Except for changing the barbituric acid to dimedone while maintaining its molar ratio, the same procedure as in Example 58 was carried out to obtain a compound represented by formula (I-3) and formula (I-77) Represents a mixture of compounds.

<Identification of the compound represented by formula (I-3)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 402

Accurate quality: 401

<Identification of the compound represented by formula (I-77)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 397

Accurate quality: 396

Example 70

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 3-oxo-3-(2-thienyl)propionitrile (manufactured by Sigma Aldrich, Japan), In the same manner as in Example 7, the compound represented by formula (I-78) was obtained.

<Identification of the compound represented by formula (I-78)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 414

Accurate quality: 413

Example 71

Except that while maintaining its molar ratio, methyl 4-cyanoacetoxybenzoate was changed to 2-furylmethylacetonitrile (manufactured by Sigma Aldrich Co., Ltd.), the same procedure was followed as in Example 7 to obtain A compound represented by formula (I-79).

<Identification of the compound represented by formula (I-79)>

(Quality analysis) Ionization mode=ESI+: m/z=[MH] ⁺ 382

Accurate quality: 381

Example 72

In addition to maintaining its molar ratio, while changing 2-chlorobenzylacetonitrile Except for changing to 3-cyanoacetoxybenzoic acid, the same procedure as in Example 58 was carried out to obtain a mixture containing the compound represented by formula (I-44) and the compound represented by formula (I-80).

<Identification of the compound represented by formula (I-9)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Accurate quality: 489

<Identification of the compound represented by formula (I-80)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 427

Accurate quality: 428

Example 73

Except that while maintaining its molar ratio, 2-chlorobenzylacetonitrile was changed to 4-cyanoacetoxybenzoic acid, the same operation as that of Example 58 was obtained to obtain a compound represented by formula (I-45) A mixture of the compound and the compound represented by formula (I-81).

<Identification of the compound represented by formula (I-45)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Accurate quality: 489

<Identification of the compound represented by formula (I-81)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 427

Accurate quality: 428

Example 74

Except for changing the phthalonitrile to 4-nitrophthalonitrile while maintaining the molar ratio, and changing the 2-chlorobenzylacetonitrile to 3-cyanoacetonitrile while maintaining the molar ratio. In the same manner as in Example 58, a compound containing the compound represented by formula (I-82) and the compound represented by formula (I-83) was obtained.

<Identification of the compound represented by formula (I-82)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 533

Accurate quality: 534

<Identification of the compound represented by formula (I-83)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 472

Accurate quality: 473

Example 75

Except for changing the phthalonitrile to 4-nitrophthalonitrile while maintaining its molar ratio, and changing the 2-chlorobenzylacetonitrile to 4-cyanoacetonitrile while maintaining its molar ratio. In the same manner as in Example 58, a mixture containing the compound represented by formula (I-84) and the compound represented by formula (I-85) was obtained.

<Identification of the compound represented by formula (I-84)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 533

Accurate quality: 534

<Identification of the compound represented by formula (I-85)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 472

Accurate quality: 473

Example 76

Except that while maintaining its molar ratio, 2-chlorobenzylacetonitrile was changed to 2-cyanoacetoxybenzoic acid, the same procedure as in Example 58 was carried out to obtain a compound containing formula (I-43) A mixture with the compound represented by formula (I-86).

<Identification of the compound represented by formula (I-43)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 488

Accurate quality: 489

<Identification of the compound represented by formula (I-86)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 427

Accurate quality: 428

Example 77

Except for changing the phthalonitrile to 4-nitrophthalonitrile while maintaining the molar ratio, and changing the 2-chlorobenzylacetonitrile to 2-cyanoacetonitrile while maintaining the molar ratio. In the same manner as in Example 58, a mixture containing the compound represented by formula (I-87) and the compound represented by formula (I-88) was obtained.

<Identification of the compound represented by formula (I-87)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 533

Accurate quality: 534

<Identification of the compound represented by formula (I-88)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 472

Accurate quality: 473

Synthesis Example 5

An appropriate amount of nitrogen was introduced into a 1-L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the atmosphere was replaced with a nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C while stirring. Next, 38 parts of acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] dec-8-yl acrylate and 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] A mixed solution of 289 parts of a mixture of dec-9-yl ester and 125 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours.

On the other hand, a mixed solution in which 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After dripping, keep at this temperature for 4 hours, then cool to room temperature, A solution of the copolymer (resin B1) with a solid content of 35.0% was obtained. The weight average molecular weight of the obtained resin B1 was 8,800, the dispersion degree was 2.1, and the solution acid value was 28 mg-KOH/g.

Synthesis Example 6

Into a 1L flask equipped with a reflux condenser, dropping funnel and agitator, an appropriate amount of nitrogen was introduced to replace the nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85°C while stirring. Next, 54 parts of acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] dec-8-yl acrylate and 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] A mixed solution of 225 parts of a mixture of dec-9-yl ester, 81 parts of ethylene toluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. On the other hand, a mixed solution in which 30 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After the starter solution was dropped, it was kept at this temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin B2) with a solid content of 37.5%.

The weight average molecular weight of the obtained resin B2 was 10,600, the dispersion degree was 2.01, and the solution acid value was 43 mg-KOH/g.

Example 78

The following components are mixed to obtain a colored composition.

Coloring agent (A): 18 parts of compound (I-2) obtained in Example 2; resin (B): 465 parts of resin B1 solution; solvent (E): 6.24 parts of propylene glycol monomethyl ether acetate; solvent ( E): 510 parts of N-methyl-2-pyrrolidone; and Surfactant: Polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.063 parts

Example 79

The following components are mixed, and the compound represented by formula (I-3) is dispersed by a bead mill to obtain a colored dispersion liquid.

Coloring agent (A): 10 parts of compound (I-3) obtained in Example 3; 7 parts of dispersant (DISPERBYK-2155; manufactured by BYK Cemie Co., Ltd., Japan); resin (B): 18.6 parts of resin B2 solution; Solvent (E): 154 parts of propylene glycol monomethyl ether acetate; and solvent (E): 10 parts of 4-hydroxy-4-methyl-2-pentanone;

Example 80

Pigment: CI Pigment Green 7 27 parts; Acrylic pigment dispersant 12.2 parts; Resin (B): Resin B2 solution 25.2 parts; and Solvent (E): Propylene glycol monomethyl ether acetate 161 parts; the above components are mixed and used The bead mill mixes the pigment dispersion in which the pigment is dispersed with the following components to obtain a colored curable resin composition.

60 parts of the colored dispersion obtained in Example 79; resin (B): 97.2 parts of resin B2 solution; polymerizable compound (C): dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku Share) system) 48 copies; Polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Corporation) 9.6 parts; solvent (E): propylene glycol monomethyl ether acetate 560 parts; and leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.15 parts;

Example 81

Pigment: CI Pigment Green 58 27 parts; Acrylic pigment dispersant 12.2 parts; Resin (B): Resin B2 solution 25.2 parts; and Solvent (E): Propylene glycol monomethyl ether acetate 161 parts; the above components are mixed and used The bead mill mixes the pigment dispersion in which the pigment is dispersed with the following components to obtain a colored curable resin composition.

60 parts of the colored dispersion obtained in Example 79; resin (B): 97.2 parts of resin B2 solution; polymerizable compound (C): dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku Stock) 48 parts; polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure( Registered trademark) OXE-01; manufactured by BASF Corporation) 9.6 parts; solvent (E): 560 parts of propylene glycol monomethyl ether acetate; and Leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.15 parts;

Example 82

Pigment: CI Pigment Green 59 27 parts; acrylic pigment dispersant 12.2 parts; resin (B): resin B2 solution 25.2 parts; and solvent (E): propylene glycol monomethyl ether acetate 161 parts; mix the above ingredients and The pigment dispersion in which the pigment is dispersed by a bead mill is mixed with the following components to obtain a colored curable resin composition.

60 parts of the colored dispersion obtained in Example 79; resin (B): 97.2 parts of resin B2 solution; polymerizable compound (C): dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku Stock) 48 parts; polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure( Registered trademark) OXE-01; manufactured by BASF Corporation) 9.6 parts; solvent (E): 560 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; Toray Dow Corning ( Share) system) 0.15 copies;

Example 83

Pigment: 36 27 parts of C.I. Pigment Green; 12.2 parts of acrylic pigment dispersant; Resin (B): 25.2 parts of resin B2 solution; and solvent (E): 161 parts of propylene glycol monomethyl ether acetate; a pigment dispersion obtained by mixing the above components and dispersing the pigment by a bead mill, and the following components Mixed to obtain a colored curable resin composition.

60 parts of the colored dispersion obtained in Example 79; resin (B): 97.2 parts of resin B2 solution; polymerizable compound (C): dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku Stock) 48 parts; polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure( Registered trademark) OXE-01; manufactured by BASF Corporation) 9.6 parts; solvent (E): 560 parts of propylene glycol monomethyl ether acetate; and leveling agent: polyether modified polysiloxane oil (Toray Silicone SH8400; Toray Dow Corning ( Share) system) 0.15 copies;

Example 84

[Making of Coloring Pattern]

The colored curable resin composition obtained in Example 80 was spin-coated on a 2-inch square glass substrate (Eagle XG; Corning Corporation), and then pre-baked at 100°C for 3 minutes to form a colored composition物层。 The material layer. After cooling, the distance between the substrate on which the coloring composition layer is formed and the quartz glass mask was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON (stock)) was used to set the gap at 80 mJ/cm ² in an atmospheric environment. Exposure amount (365nm reference) Exposure. In addition, as for the photomask, a line and space pattern of 100 μm is formed. At 25° C., the coloring composition layer after exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 70 seconds for development, and washed with water.

The colored coating film was post-baked at 230°C for 30 minutes to obtain a colored pattern.

Example 85

Except that the coloring curable resin composition obtained in Example 80 was changed to the coloring curable resin composition obtained in Example 81, the same procedure as in Example 84 was carried out to obtain a colored pattern.

Example 86

Except that the coloring curable resin composition obtained in Example 80 was changed to the coloring curable resin composition obtained in Example 82, the same procedure as in Example 84 was carried out to obtain a colored pattern.

Example 87

Except that the coloring curable resin composition obtained in Example 80 was changed to the coloring curable resin composition obtained in Example 83, the same procedure as in Example 84 was carried out to obtain a colored pattern.

Synthesis Example 7

At -78°C, acetonitrile with a molar number of 4 times the molar number of 10 parts of methyl 4-(carboxymethyl)benzoate and 10 parts of methyl 4-(carboxymethyl)benzoate with a molar number of 10 A mixture of 130 parts of lithium bis(trimethylsilyl)amide and 130 parts of tetrahydrofuran that is 3 times the number of moles.

In this mixture, add 10 parts of methyl 4-(carboxymethyl)benzoate and A mixture of 90 parts of tetrahydrofuran was stirred from -78°C to room temperature for 16 hours.

The obtained mixture was refined to obtain 8 parts of 4-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene.

<Identification of 4-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 202

Accurate quality: 203

Synthesis Example 8

At -78°C, acetonitrile with a molar number of 33 parts of methyl 4-(2-carboxyethyl)benzoate 6 times the molar number and 4-(2-carboxyethyl)benzene with a molar number of A mixture of 33 parts of methyl formate and 890 parts of lithium bis(trimethylsilyl)amide and 890 parts of tetrahydrofuran.

To this mixture, 33 parts of methyl 4-(carboxyethyl)benzoate was added, and the mixture was stirred at -78°C for 30 minutes. The obtained mixture was refined to obtain 29 parts of 4-(2-carboxyethyl)-1-(cyanomethylcarbonyl)benzene.

<Identification of 4-(2-carboxyethyl)-1-(cyanomethylcarbonyl)benzene>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 216

Accurate quality: 217

Synthesis Example 9

At -78°C, acetonitrile with a molar number of 30 parts of methyl 2-(carboxymethyl)benzoate 4 times the molar number and 2-(carboxymethyl)benzoic acid with a molar number of A mixture of 270 parts of lithium bis(trimethylsilyl)amide and 270 parts of tetrahydrofuran which are three times the molar number of 30 parts of methyl ester. To this mixture, a mixture of 30 parts of methyl 2-(carboxymethyl)benzoate and 270 parts of tetrahydrofuran was added, and the mixture was stirred from -78°C to room temperature for 3 hours. The obtained mixture was refined to obtain 27 parts of 2-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene.

<Identification of 2-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 202

Accurate quality: 203

Synthesis Example 10

At -78°C, acetonitrile with a molar number of 34 parts of 4-(2-methoxycarbonyl)ethyl)benzoic acid and 6 times the molar number of 4-(2-methoxy) benzoic acid was obtained. A mixture of 34 parts of lithium bis(trimethylsilyl)amide and 1,200 parts of tetrahydrofuran, which is 5.5 times the molar number of 34 parts of carbonyl)ethyl)benzoic acid.

To this mixture, 34 parts of 4-(2-methoxycarbonyl)ethyl)benzoic acid was added, and the mixture was stirred at -78°C for 1 hour. The obtained mixture was recrystallized and refined with ethyl acetate and hexane to obtain 30 parts of 4-(2-(cyanomethylcarbonyl)ethyl)benzoic acid.

<Identification of 4-(2-(cyanomethylcarbonyl)ethyl)benzoic acid>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 216

Accurate quality: 217

Synthesis Example 11

At -78°C, acetonitrile with a molar number of 5.5 times the molar number of 28 parts of 4-(methoxycarbonylmethyl)benzoic acid and 4-(methoxycarbonylmethyl)benzoic acid with a molar number of 4-(methoxycarbonylmethyl)benzoic acid was obtained 28 parts of a mixture of n-butyllithium 5 times the number of moles and 1,100 parts of tetrahydrofuran. To this mixture, 28 parts of 4-(methoxycarbonylmethyl)benzoic acid was added, and the mixture was stirred at -78°C for 15 minutes. The obtained mixture was purified by column chromatography to obtain 22 parts of 4-(cyanomethylcarbonylmethyl)benzoic acid.

<Identification of 4-(cyanomethylcarbonylmethyl)benzoic acid>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 202

Accurate quality: 203

Synthesis Example 12

At -78°C, acetonitrile with a molar number of 18 parts of 4-(methoxycarbonyl)-3-methoxybenzoic acid and 4 times the molar number of 4-(methoxycarbonyl) was obtained. ) A mixture of 18 parts of 3-methoxybenzoic acid and 160 parts of tetrahydrofuran of lithium bis(trimethylsilyl)amide which is 3 times the number of moles.

To this mixture, a mixture of 18 parts of 4-(methoxycarbonyl)-3-methoxybenzoic acid and 160 parts of tetrahydrofuran was added, and the mixture was stirred at -78°C to room temperature for 16 hours.

The obtained mixture was refined to obtain 15 parts of 4-(cyanomethoxycarbonyl)-3-methoxybenzoic acid.

<Identification of 4-(cyanomethoxycarbonyl)-3-methoxybenzoic acid>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 218

Accurate quality: 219

Synthesis Example 13

At -78°C, acetonitrile with a molar number of 14 parts of 4-(methoxycarbonyl)-2-methoxybenzoic acid and four times the molar number of 4-(methoxycarbonyl) was obtained. ) A mixture of 14 parts of 2-methoxybenzoic acid with 3 times the number of moles of lithium bis(trimethylsilyl)amide and 120 parts of tetrahydrofuran.

To this mixture, a mixture of 14 parts of 4-(methoxycarbonyl)-2-methoxybenzoic acid and 120 parts of tetrahydrofuran was added, and the mixture was stirred from -78°C to room temperature for 16 hours.

The obtained mixture was refined to obtain 13 parts of 4-(cyanomethylcarbonyl)-2-methoxybenzoic acid.

<Identification of 4-(cyanomethylcarbonyl)-2-methoxybenzoic acid>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 218

Accurate quality: 219

Example 88

Mix 5 parts of 4-aminophthalonitrile and 40 parts of methanol.

While maintaining the temperature below 5°C, a 25% sodium methoxide methanol solution containing 5 parts of 4-aminophthalonitrile in moles and 0.5 times the mole of sodium methoxide was added to the obtained mixture. This mixture was stirred at 5°C for 3 hours, Stir at room temperature for 16 hours.

To the obtained mixture, benzylacetonitrile and 5.3 parts of acetic acid having a molar number 2.2 times the molar number of 5 parts of 4-aminophthalonitrile were added. The mixture was stirred at room temperature for 32 hours. After distilling the solvent off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-89).

<Identification of the compound represented by formula (I-89)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 417

Accurate quality: 416

Example 89

5 parts of 4-(N-acetamido)phthalonitrile and 40 parts of methanol were mixed.

While keeping it below 5°C, add 25% sodium methoxide containing 5 parts of 4-(N-acetamido)phthalonitrile with a molar number of 0.5 times the molar number of sodium methoxide to the obtained mixture. Solution.

The mixture was stirred at 5°C for 3 hours and at room temperature for 16 hours.

To the obtained mixture, benzylacetonitrile and 5.3 parts of acetic acid having a molar number of 5 parts of 4-(N-acetamido)phthalonitrile and 2.2 times the molar number of 5 parts of 4-(N-acetylamino)phthalonitrile were added.

The mixture was stirred at room temperature for 16 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.2 part of the compound represented by formula (I-90).

<Identification of the compound represented by formula (I-90)>

(Quality analysis) Ionization mode=ESI+: m/z=[MH] ⁺ 459

Accurate quality: 458

Example 90

3 parts of 4-carbonylphthalonitrile and 32 parts of methanol were mixed.

At room temperature, a 21% sodium ethoxide ethanol solution containing 3 parts of 4-carboxyphthalonitrile with a molar number of 2.1 times the molar number of sodium ethoxide was added to the obtained mixture.

The mixture was stirred at 60°C for 16 hours.

To the obtained mixture, 9.4 parts of benzylacetonitrile and 9.4 parts of acetic acid having a molar number 2.3 times the molar number of 3 parts of 4-carboxyphthalonitrile were added.

The mixture was stirred at 90°C for 20 hours. 9.4 parts of acetic acid was added to the obtained mixture. The mixture was stirred at 90°C for 72 hours. After the obtained mixture was distilled to remove the solvent with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.5 part of the compound represented by formula (I-91).

<Identification of the compound formula represented by formula (I-91)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 444

Accurate quality: 445

Example 91

3 parts of 4-carboxyphthalonitrile and 47 parts of ethanol were mixed. At room temperature, to the obtained mixture, a 25% sodium methoxide methanol solution containing 3 parts of 4-carboxyphthalonitrile in moles of sodium methoxide twice the number of moles is added.

The mixture was stirred at 60°C for 16 hours.

To the obtained mixture, 9.4 parts of acetic acid, 2.3 times the molar number of 4-cyanoacetonitrile to 3 parts of 4-carboxyphthalonitrile, and 120 parts of methanol were added.

The mixture was stirred at 70°C for 96 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.2 part of the compound represented by formula (I-92).

<Identification of the compound represented by formula (I-92)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 532

Accurate quality: 533

Example 92

3 parts of 4.5-dichlorophthalonitrile and 48 parts of methanol were mixed.

While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution of sodium methoxide with a molar number of 3 parts of 4.5-dichlorophthalonitrile and 1 times the molar number was added to the obtained mixture.

The mixture was stirred at room temperature for 16 hours.

To the obtained mixture, 6.3 parts of acetic acid, 3 parts of 4.5-dichlorophthalonitrile with a molar number of 2.2 times the molar number of 4-cyanoacetoxybenzoic acid and 160 parts of methanol were added.

The mixture was stirred at room temperature for 48 hours and at 50°C for 16 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.6 part of the compound represented by formula (I-93).

<Identification of the compound represented by formula (I-93)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 556

Accurate quality: 557

Example 93

5 parts of 4-methoxyphthalonitrile and 79 parts of methanol were mixed.

While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 5 parts of 4-methoxyphthalonitrile in moles of sodium methoxide 2.5 times the number of moles was added to the obtained mixture.

The mixture was stirred at room temperature for 3 hours and at 65°C for 3 hours.

To the obtained mixture, 160 parts of 4-cyanoacetoxybenzoic acid and 21 parts of acetic acid were added with a molar number 2.2 times the molar number of 5 parts of 4-methoxyphthalonitrile.

The mixture was stirred at room temperature for 64 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.6 part of the compound represented by formula (I-94).

<Identification of the compound represented by formula (I-94)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 518

Accurate quality: 519

Example 94

5 parts of 4-methoxyphthalonitrile and 79 parts of methanol were mixed.

While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 5 parts of 4-methoxyphthalonitrile in moles of sodium methoxide twice the number of moles was added to the obtained mixture. The mixture was stirred at 70°C for 5 hours.

To the obtained mixture, 3-cyanoacetoxybenzoic acid having a molar number 2.5 times the molar number of 5 parts of 4-methoxyphthalonitrile, 160 parts of methanol, and 21 parts of acetic acid were added.

The mixture was stirred at room temperature for 68 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.6 part of the compound represented by formula (I-95).

<Identification of the compound represented by formula (I-95) (compound 21-168)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 518

Accurate quality: 519

Example 95

8 parts of 4-methoxyphthalonitrile and 95 parts of methanol were mixed.

At room temperature, a 25% sodium methoxide methanol solution containing 8 parts of 4-methoxyphthalonitrile and 2.5 times the number of moles of sodium methoxide was added to the obtained mixture.

The mixture was stirred at 65°C for 3 hours.

To the obtained mixture, 34 parts of 2-cyanoacetoxybenzoic acid and 34 parts of acetic acid having a molar number 2.2 times the molar number of 8 parts of 4-methoxyphthalonitrile were added.

The mixture was stirred at room temperature for 16 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.4 part of the compound represented by formula (I-96).

<Identification of the compound represented by formula (I-96) (compound 21-167)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 518

Accurate quality: 519

Example 96

Mix 2 parts of 4-carboxyphthalonitrile and 32 parts of methanol.

While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 2 parts of 4-carboxyphthalonitrile in moles of sodium methoxide twice the number of moles was added to the obtained mixture.

The mixture was stirred at 60°C for 6 hours.

To the obtained mixture, 4.2 parts of acetic acid, 2.2 times the number of moles of 2 parts of 4-carboxyphthalonitrile, 4-(carboxymethyl)-1-(cyanomethylcarbonyl)benzene and methanol were added. 95 copies.

The mixture was stirred at 70°C for 16 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-97).

<Identification of the compound represented by formula (I-97)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 560

Accurate quality: 561

Example 97

6.51 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 58 parts of methanol were mixed.

While keeping the temperature at 5°C or lower, a mixture of 7.61 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 71 parts of methanol was dropped over 1 hour and 30 minutes into the obtained mixture. The mixture was stirred below 5°C for 12 hours. While maintaining the temperature below 5°C, 15.0 parts of acetic acid was added to the obtained mixture, and 30.2 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 927 parts of methanol were added.

After the obtained mixture was stirred at room temperature for 4 hours, it was stirred at 40°C for 96 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.882 parts of the compound represented by formula (I-4).

<Identification of the compound represented by formula (I-4)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 470

Accurate quality: 469

Example 98

5.44 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 64 parts of methanol were mixed.

While keeping the temperature at 5°C or lower, a mixture of 6.37 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 48 parts of methanol was dropped in the obtained mixture over 1 hour and 30 minutes. The obtained mixture was stirred for 12 hours while maintaining the temperature below 5°C. Keep on At 5°C or less, 4.20 parts of acetic acid, 742 parts of methanol, and 7.69 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture. The obtained mixture was stirred at room temperature for 36 hours.

0.482 parts of acetic acid and 0.775 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture, and the mixture was stirred at room temperature for 3 hours and at 40°C for 12 hours.

To the obtained mixture, 0.638 parts of acetic acid and 1.15 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 40°C for 6 hours. To the obtained mixture, 0.549 parts of acetic acid and 0.958 parts of 2-chlorobenzylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 40°C for 36 hours. 4.17 parts of acetic acid and 5.96 parts of barbituric acid were added to the obtained mixture, and it stirred at 40 degreeC for 48 hours. 2.08 parts of acetic acid and 2.72 parts of barbituric acid were added to the obtained mixture, and it stirred at 40 degreeC for 24 hours.

After distilling the solvent off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.283 parts of the compound represented by formula (I-63).

<Identification of the compound represented by formula (I-63)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 419

Accurate quality: 418

Example 99

Combine 7.51 parts of 4,5-dichlorophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) with methanol 130 parts are mixed.

While maintaining the temperature at 0°C, 7.41 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 1 hour and 30 minutes into the obtained mixture.

The obtained mixture was stirred at room temperature for 16 hours.

At room temperature, 16.0 parts of acetic acid, 670 parts of methanol, and 7.27 parts of 4-cyanoacetoxybenzoic acid were added to the obtained mixture.

The obtained mixture was stirred at room temperature for 12 hours and at 50°C for 12 hours.

To the obtained mixture, 0.433 parts of acetic acid and 0.733 parts of 4-cyanoacetoxybenzoic acid were added, and the mixture was stirred at 50°C for 6 hours. 0.573 parts of acetic acid and 1.09 parts of 4-cyanoacetoxybenzoic acid were added to the obtained mixture, and it stirred at 50 degreeC for 6 hours. To the obtained mixture, 0.493 parts of acetic acid and 0.906 parts of 4-cyanoacetoxybenzoic acid were added, and the mixture was stirred at 50°C for 12 hours. To the obtained mixture, 3.75 parts of acetic acid and 5.35 parts of barbituric acid were added, and the mixture was stirred at 50°C for 24 hours. To the obtained mixture, 1.87 parts of acetic acid and 2.44 parts of barbituric acid were added, and the mixture was stirred at 50°C for 24 hours. After distilling the solvent off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.252 parts of the compound represented by formula (I-98).

<Identification of the compound represented by formula (I-98)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 495

Exact quality: 496

Example 100

Except for keeping its molar ratio, while changing 2-chlorobenzylacetonitrile to 4-cyanoacetoxybenzoic acid, while keeping its molar ratio, changing barbituric acid to benzylacetonitrile Except for the above, the same procedure as in Example 98 was carried out to obtain the compound represented by formula (I-99).

<Identification of the compound represented by formula (I-99)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 444

Accurate quality: 445

Example 101

In addition to changing the phthalonitrile to 4-nitrophthalonitrile while maintaining its molar ratio, while maintaining its molar ratio, the 2-chlorobenzylacetonitrile was changed to 4-cyanoacetonitrile, While maintaining its molar ratio, the barbituric acid was changed to benzylacetonitrile, and otherwise in the same manner as in Example 98, the compound represented by formula (I-100) was obtained.

<Identification of the compound represented by formula (I-100)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 489

Accurate quality: 490

Example 102

Except for changing the barbituric acid to benzylacetonitrile while maintaining its molar ratio, the same procedure as in Example 99 was carried out to obtain the compound represented by formula (I-101).

<Identification of the compound represented by formula (I-101)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 512

Accurate quality: 513

Example 103

Except for maintaining its molar ratio, while changing 2-chlorobenzylacetonitrile to 2-cyanoacetoxybenzoic acid, while maintaining its molar ratio, changing barbituric acid to benzylacetonitrile Except for the above, the same procedure as in Example 98 was carried out to obtain the compound represented by formula (I-102).

<Identification of the compound represented by formula (I-102)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 444

Accurate quality: 445

Example 104

Except that while maintaining its molar ratio, phthalonitrile was changed to 4-nitrophthalonitrile, and 2-chlorobenzylacetonitrile was changed to 2-cyanoacetoxybenzoic acid while maintaining its molar ratio. Except for changing the barbituric acid to benzylacetonitrile, the same procedure as in Example 98 was carried out to obtain the compound represented by formula (I-103).

<Identification of the compound represented by formula (I-103)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 489

Accurate quality: 490

Example 105

Except that while maintaining its molar ratio, 4-cyanoacetoxybenzoic acid was changed to 2-cyanoacetoxybenzoic acid, while maintaining its molar ratio, barbituric acid was changed to benzyloxy Except for acetonitrile, the same procedures as in Example 99 were carried out to obtain the compound represented by formula (I-104).

<Identification of the compound represented by formula (I-104) (compound 01-151)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 512

Accurate quality: 513

Example 106

3 parts of 4-bromophthalonitrile and 24 parts of methanol were mixed.

While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 3 parts of 4-bromophthalonitrile and 0.5 times the molar number of sodium methoxide was added to the obtained mixture.

The mixture was stirred at 0°C for 3 hours.

To the obtained mixture, 3.1 parts of 4-cyanoacetoxybenzoic acid and 3.1 parts of acetic acid having a molar number of 2.2 times the molar number of 3 parts of 4-bromophthalonitrile were added.

The mixture was stirred at room temperature for 16 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-105).

<Identification of the compound represented by formula (I-105)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 566

Accurate quality: 567

Example 107

5 parts of 3,4-dicyanobenzenesulfonic acid and 79 parts of methanol were mixed.

While keeping it at 0°C, sodium methoxide containing 5 parts of 3,4-dicyanobenzenesulfonic acid with a molar number of 0.5 times the molar number was added to the obtained mixture The 25% methanol solution of sodium methoxide.

The mixture was stirred at 0°C for 6 hours.

To the obtained mixture, 5.2 parts of 4-cyanoacetoxybenzoic acid and 5.2 parts of acetic acid having a molar number of 5 parts of 3,4-dicyanobenzenesulfonic acid that were 2.2 times the molar number were added.

The mixture was stirred at room temperature for 16 hours.

After distilling the solvent off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.4 part of the compound represented by formula (I-106).

<Identification of the compound represented by formula (I-106)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 568

Accurate quality: 569

Example 108

Mix 2 parts of phthalonitrile and 16 parts of methanol.

While maintaining the temperature at 5°C, a 25% sodium methoxide methanol solution containing sodium methoxide 0.5 times the number of moles of 2 parts of phthalonitrile was added to the obtained mixture.

The mixture was stirred at 5°C for 3 hours.

To the obtained mixture, N-acetyl-4-(cyanoacetoxy)aniline having a molar number 2.2 times the molar number of 2 parts of phthalonitrile and 2.2 parts of acetic acid were added.

The mixture was stirred at room temperature for 16 hours.

To the obtained mixture, N-acetyl-4-(cyanoacetoxy)aniline having a molar number 1.1 times the molar number of 2 parts of phthalonitrile was added.

The mixture was stirred at room temperature for 16 hours and at 50°C for 48 hours.

After the obtained mixture was distilled to remove the solvent with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-107).

<Identification of the compound represented by formula (I-107)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 516

Accurate quality: 515

Example 109

Mix 2 parts of 4-(trifluoromethyl)phthalonitrile and 32 parts of methanol.

While keeping the temperature at 0°C, a 25% sodium methoxide methanol solution containing 2 parts of 4-(trifluoromethyl)phthalonitrile in moles of sodium methoxide 0.8 times the mole number was added to the obtained mixture.

The mixture was stirred at 10°C for 2 hours.

To the obtained mixture, 4.4 parts of acetic acid and 2-parts of 4-(trifluoromethyl)phthalonitrile with a molar number of 2.2 times the molar number of 4-cyanoacetoxybenzoic acid were added.

The mixture was stirred at room temperature for 16 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, The obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-108).

<Identification of the compound represented by formula (I-108)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 556

Accurate quality: 557

Example 110

4 parts of 4-(trifluoromethyl)phthalonitrile and 32 parts of methanol were mixed.

While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 4 parts of 4-(trifluoromethyl)phthalonitrile in moles and 0.5 times the mole number of sodium methoxide was added to the obtained mixture.

The mixture was stirred at 0°C for 3 hours.

To the obtained mixture, 4.4 parts of 3-cyanoacetoxybenzoic acid and 4.4 parts of acetic acid whose molar number is 2.2 times the molar number of 4 parts of 4-(trifluoromethyl)phthalonitrile are added.

The mixture was stirred at room temperature for 16 hours.

After distilling the solvent off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-109).

<Identification of the compound represented by formula (I-109)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 556

Accurate quality: 557

Example 111

2.5 parts of 4-(trifluoromethyl)phthalonitrile and 79 parts of methanol were mixed.

While maintaining the temperature at 0°C, a 25% sodium methoxide methanol solution containing 2.5 parts of 4-(trifluoromethyl)phthalonitrile and 0.5 times the molar number of sodium methoxide was added to the obtained mixture.

The mixture was stirred at 0°C for 3 hours.

To the obtained mixture, 2.5 parts of 4-(trifluoromethyl)phthalonitrile in molar number 2.2 times the molar number of 2-cyanoacetoxybenzoic acid and 3 parts of acetic acid were added.

The mixture was stirred at room temperature for 16 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.1 part of the compound represented by formula (I-110).

<Identification of the compound represented by formula (I-110)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 556

Accurate quality: 557

Example 112

Mix 2 parts of phthalonitrile and 16 parts of methanol.

While maintaining at 5°C, a 25% sodium methoxide methanol solution containing sodium methoxide 0.5 times the number of moles of 2 parts of phthalonitrile was added to the obtained mixture.

The mixture was stirred at 5°C for 3 hours and at room temperature for 16 hours.

To the obtained mixture, 4-sulfamoyl acetonitrile having a molar number 2.2 times the molar number of 2 parts of phthalonitrile and 2.2 parts of acetic acid were added.

The mixture was stirred at room temperature for 16 hours.

After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.3 part of the compound represented by formula (I-42).

<Identification of the compound represented by formula (I-42)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 560

Exact quality: 559

Example 113

4.1 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 48 parts of methanol were mixed.

While keeping the temperature below 5°C, 4.8 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained mixture A mixture of 36 parts of methanol was dropped over 1 hour and 30 minutes. While keeping the obtained mixture at 5°C or lower, it was stirred for 12 hours.

While keeping the temperature at 5°C or lower, 5.1 parts of acetic acid, 750 parts of methanol, and 7.2 parts of 4-sulfamoylbenzylacetonitrile were added to the obtained mixture.

The obtained mixture was stirred at room temperature for 36 hours. To the obtained mixture were added 0.56 parts of acetic acid and 0.73 parts of 4-sulfamoylbenzylacetonitrile, and stirred at room temperature for 3 hours and at 40°C for 12 hours. To the obtained mixture were added 0.77 parts of acetic acid and 1.1 parts of 4-sulfamoylbenzylacetonitrile, and stirred at 40°C for 6 hours.

To the obtained mixture were added 0.66 parts of acetic acid and 0.90 parts of 4-sulfamoylbenzylacetonitrile, and stirred at 40°C for 36 hours. 3.1 parts of acetic acid and 4.5 parts of barbituric acid were added to the obtained mixture, and the mixture was stirred at 40°C for 48 hours.

1.6 parts of acetic acid and 2.0 parts of barbituric acid were added to the obtained mixture, and it stirred at 40 degreeC for 24 hours. After the solvent was distilled off the obtained mixture with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 0.21 part of the compound represented by formula (I-111).

<Identification of the compound represented by formula (I-111)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 464

Accurate quality: 463

Example 114

Except for maintaining its molar ratio, while changing phthalonitrile to 4-nitrophthalein Except for the nitrile, the same procedures as in Example 113 were carried out to obtain the compound represented by formula (I-112).

<Identification of the compound represented by formula (I-112)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 509

Accurate quality: 508

Example 115

Except for changing the phthalonitrile to 4-nitrophthalonitrile while maintaining its molar ratio, the same procedure as in Example 108 was carried out to obtain the compound represented by formula (I-113).

<Identification of the compound represented by formula (I-113)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 561

Accurate quality: 560

Example 116

Except for changing the phthalonitrile to 4-nitrophthalonitrile while maintaining its molar ratio, the same procedure as in Example 112 was carried out to obtain the compound represented by formula (I-114).

<Identification of the compound represented by formula (I-114)>

(Quality analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 605

Accurate quality: 604

Example 117

Except that while keeping its molar ratio, 4-cyanoacetoxybenzoic acid was changed to 2-cyanoacetoxybenzoic acid, the rest was carried out in the same manner as in Example 106 to obtain the formula (I-115) Compound.

<Identification of the compound represented by formula (I-115)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 566

Accurate quality: 567

Example 118

Except that while maintaining its molar ratio, 4-cyanoacetoxybenzoic acid was changed to 3-cyanoacetoxybenzoic acid, the rest was carried out in the same manner as in Example 106 to obtain the formula (I-116) Compound.

<Identification of the compound represented by formula (I-116)>

(Mass spectrometry) ionization mode = ESI: m / z = [ MH] - 566

Accurate quality: 567

Example 119

Except for changing the barbituric acid to dimethanone (manufactured by Tokyo Chemical Industry Co., Ltd.) while maintaining its molar ratio, the same procedure as in Example 99 was carried out to obtain the compound represented by formula (I-117).

<Identification of the compound represented by formula (I-117)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 507

Accurate quality: 508

Example 120 to Example 171

Except that phthalonitrile was changed to a compound represented by formula (PPA-1) having the group shown in the column "B1B2" of Table 10, and 2-chlorobenzylacetonitrile was changed to have the column "Lk" of Table 10 and " Except for the compound represented by the formula (PPA-2) of the group shown in the "Hd" column, the rest was carried out in the same manner as in Example 97 to obtain the compound represented by the formula (PPA-3) having the substituents described in the respective columns.

The identification of compounds is carried out by mass analysis. The example described in "1" in the "Ionization Mode" column shows the (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ detected value in the "Detection Value" column . "Ionization mode" column of the table on the next page of the embodiment of "-1", the system via (mass spectrometry) ionization mode = ESI-: m / z = [ MH] - the values detected are shown in Table 10 in the "Detection Value" column. The "Accurate Mass" column in Table 10 indicates the precise mass value.

In Table 10, the symbols (HH35, BB19, etc.) in the "B1B2" column and the "Hd" column have the same definitions as those in Table 1 to Table 9(b) in the specification of this case, except for the following symbols .

In the above table, HHJ5, HHJ6, HHJ7, HHJ10, HHJ14, HHJ15, HHk5, HHk6, HHk7 respectively represent the formula (HHJ5), formula (HHJ6), formula (HHJ7), formula (HHJ10), formula (HHJ14), The formula (HHJ15), the formula (HHk5), the formula (HHk6) and the formula (HHk7) represent the base.

Example 172 to Example 187

Except that 4-cyanoacetoxybenzoic acid was changed to a compound represented by the formula (PPA-2) having the groups shown in the "Lk" column and the "Hd" column of Table 11, the rest was the same as in Example 92 To obtain a compound represented by formula (I-93a) having the substituents described in each column above.

The identification of compounds is carried out by mass analysis. The results of each mass analysis are described in Table 11 with the same points as in Example 120 to Example 171.

In Table 11, the symbols (HH35, etc.) described in the "Hd" column can be defined as the same as those in Table 1 to Table 9(b) in the specification of this case. HHk7 represents the base represented by the above formula (HHk7).

Example 188 to Example 229

Except that phthalonitrile was changed to a compound represented by formula (PPA-1) having the group shown in the column "B1B2" of Table 12, and 2-chlorobenzylacetonitrile was changed to have the column "Lk" of Table 12 and Except for the compound represented by the formula (PPA-2) of the group shown in the "Hd" column, the rest was performed in the same manner as in Example 98 to obtain the compound represented by the formula (I-63a) having the substituents described in each column.

The identification of compounds is carried out by mass analysis. The results of each quality analysis are described in the table with the same points as in Example 120 to Example 171 12 in.

In Table 12, the symbols described in the "B1B2" column and the "Hd" column have the same definitions as those in Table 1 to Table 9(b) in the specification of this case, except for the following symbols. HHk7 represents the group represented by the above formula (HHk7).

Example 230 to Example 243

Except that 4-cyanoacetoxybenzoic acid was changed to a compound represented by the formula (PPA-2) having the group shown in the "Lk" column and the "Hd" column of Table 13, the rest was the same as in Example 99, The compound represented by formula (I-98a) having the substituents described in each column above is obtained.

The identification of compounds is carried out by mass analysis. The results of each mass analysis are described in Table 13 with the same points as in Example 120 to Example 171.

In Table 13, the symbols described in the "Hd" column have the same definitions as those in Table 1 to Table 9(b) in the specification of this case, except for the following symbols. HHk7 represents the group represented by the above formula (HHk7).

Example 244 to Example 246

Except that phthalonitrile was changed to a compound represented by formula (PPA-1) having the group shown in the column "B1B2" of Table 14, the 2-chlorobenzylacetonitrile was changed to have the column "Lk" and "Hd" in Table 14 The compound represented by the formula (PPA-2) shown in the column, and the barbituric acid was changed to dimethanone, the rest was the same as in Example 98 to obtain the formula having the substituents described in the above columns The compound represented by (I-63b).

The identification of compounds is carried out by mass analysis. The results of each mass analysis are described in Table 14 with the same points as in Example 120 to Example 171.

In Table 14, the symbols in the "B1B2" column and the "Hd" column have the same definitions as the symbols in Table 1 to Table 9(b) in the specification of this case.

Example 247

In addition to maintaining its molar ratio, while changing 2-chlorobenzylacetonitrile It was changed to 3-cyanoacetoxybenzoic acid, and barbituric acid was changed to benzylacetonitrile while maintaining its molar ratio, and the rest was performed in the same manner as in Example 98 to obtain formula (I-118) Represents the compound.

<Identification of the compound represented by formula (I-118)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 444

Accurate quality: 445

Example 248

In addition to changing the phthalonitrile to 4-nitrophthalonitrile while maintaining its molar ratio, while maintaining its molar ratio, changing 2-chlorobenzylacetonitrile to 3-cyanoacetonitrile, While maintaining its molar ratio, the barbituric acid was changed to benzylacetonitrile, and otherwise in the same manner as in Example 98, the compound represented by formula (I-119) was obtained.

<Identification of the compound represented by formula (I-119)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 489

Accurate quality: 490

Example 249

Except for maintaining its molar ratio, while adding 4-cyanoacetoxybenzoic acid It was changed to 3-cyanoacetoxybenzoic acid, and barbituric acid was changed to benzylacetonitrile while maintaining its molar ratio. The rest was performed in the same manner as in Example 99 to obtain the formula (I-120) Represents the compound.

<Identification of the compound represented by formula (I-120)>

(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 512

Accurate quality: 513

Synthesis Example 14

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was poured into it, replaced with a nitrogen atmosphere, and 350 parts of propylene glycol monomethyl ether acetate was added, and heated to 85°C while stirring. Then, 70 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ]dec-8-yl acrylate or/and 3,4-epoxytricyclo [5.2. 1.0 A mixed solution of 202 parts of a mixture of ^2,6 ]dec-9-yl ester, 78 parts of ethylene toluene (isomer mixture), and 100 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution in which 33 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 167 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After the starter solution was dropped, it was kept at this temperature for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B5) with a solid content of 38.1%. The weight average molecular weight (Mw) of the obtained resin B5 was 10,400, the dispersion degree was 2.03, and the solution acid value was 53 mg-KOH/g.

Example 250

Pigment: CI Pigment Green 58 60 parts, acrylic pigment dispersant 8.1 parts, resin (B): resin B5 solution 73 parts, and solvent (E): propylene glycol monomethyl ether acetate 290 parts. Mix the above ingredients and use The bead mill prepares a pigment dispersion liquid (colorant (A1) containing liquid) in which the pigment is dispersed. In addition, colorant (A): 50 parts of compound of formula (I-45), 58 parts of dispersant, resin (B): 93 parts of resin B2 solution, and solvent (E): propylene glycol monomethyl ether acetate 800 The above-mentioned components are mixed together, and the compound of formula (I-45) is dispersed using a bead mill to obtain a colored composition. Next, the total amount of the obtained pigment dispersion liquid (colorant (A1) containing liquid); 400 parts of the obtained coloring composition; resin (B): 45 parts of resin B1 solution; polymerizable compound (C): dineopentaerythritol Hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 25 parts; polymerization initiator (D): N-benzyloxy-1-(4-phenylhydrothiophenyl) ) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF (Stock)) 15 parts; solvent (E): propylene glycol monomethyl ether acetate 86 parts; and leveling Agent: polyether modified polysiloxane oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.12 parts; The above components are mixed to obtain a colored curable resin composition 1.

[Making of Coloring Pattern]

The colored curable resin composition 1 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Corporation) by spin coating, and then pre-baked at 100°C for 3 minutes to form a colored curable resin composition layer . After cooling, the distance between the substrate on which the coloring composition layer was formed and the quartz glass mask was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used at 80 mJ/cm ² in an atmospheric environment. The exposure amount (365nm benchmark) exposure. In addition, as for the photomask, a line and space pattern of 100 μm is formed. At 25° C., the exposed colored composition layer was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 70 seconds to develop the image, and then washed with water. The colored curable resin composition layer was post-baked at 230°C for 30 minutes to obtain a colored pattern.

[Determination of phase difference]

The colored curable resin composition 1 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Corporation) by spin coating, and then pre-baked at 100°C for 3 minutes to form a colored curable resin composition layer . After cooling, the colored curable resin composition layer was exposed using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) in an atmospheric environment with an exposure amount of 80 mJ/cm ² (365 nm standard). At 25° C., the exposed colored composition layer was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 70 seconds to develop the image, and then washed with water. The colored curable resin composition layer was post-baked at 230°C for 30 minutes to obtain a colored pattern.

Use DEKTAK3 (Japan Vacuum Technology Co., Ltd.) to measure the coloration obtained The thickness of the coating film. Using an ellipsometer (M-220 spectroscopic ellipsometer; manufactured by JASCO Corporation), the retardation value in the tilt angle of this colored coating film was measured at 45°. For the measurement of the retardation value, light with a wavelength of 550 nm was used. The results are shown in Table 15.

Example 251 to Example 480

Except that the compound represented by formula (I-45) was replaced with the compound shown in the "Compound" column of Table 15, the rest was the same as in Example 250 to obtain the coloration shown in the "Colored curable resin composition" column of Table 15 Curable resin composition to obtain a colored pattern. Furthermore, in the same manner as in Example 250, a colored coating film was obtained, and the film thickness measurement and the phase difference value measurement were performed. The results are shown in Table 15.

Example 481 to Example 711

Except that the compound represented by formula (I-45) was replaced with the compound shown in the "Compound" column of Table 16, and CI Pigment Green 58 was replaced with CI Pigment Green 7, the rest was performed in the same manner as in Example 250 to obtain the table The colored curable resin composition indicated in the "Colored Curable Resin Composition" column of 16 obtains a colored pattern. Furthermore, in the same manner as in Example 250, a colored coating film was obtained, and the film thickness measurement and the phase difference value measurement were performed. The results are shown in Table 16.

Example 712 to Example 942

Except that the compound represented by formula (I-45) was replaced with the compound shown in the "Compound" column of Table 17, and CI Pigment Green 58 was replaced with CI Pigment Green 59, the rest was performed in the same manner as in Example 250 to obtain Table 17 The colored curable resin composition indicated in the column of "coloring curable resin composition" obtains a colored pattern. At the same time, in the same manner as in Example 250, a colored coating film was obtained, and the film thickness measurement and the phase difference value measurement were performed. The results are shown in Table 17.

Comparative example 1 to comparative example 3

Except that the compound represented by formula (I-45) is changed to CI Pigment Yellow 185, the dispersant of the coloring composition is changed to a dispersant (BYK-LPN6919; manufactured by BYK Chemie, Japan), and CI Pigment Green 58 is changed to Table 18 Except for the pigment indicated in the "Pigment" column, the rest was the same as in Example 250 to obtain the colored curable resin composition indicated in the "Colored curable resin composition" column of Table 18 to obtain a colored pattern. Furthermore, in the same manner as in Example 250, a colored coating film was obtained, and the film thickness measurement and the phase difference value measurement were performed. The results are shown in Table 18.

From the above results, it can be seen that the colored coating film formed from the colored curable resin composition containing the compound of the present invention is compared with the colored coating film formed from the colored curable resin composition containing CI Pigment Yellow 185. The phase difference value becomes smaller.

[Possibility of industrial application]

The coloring composition and compound of the present invention can be applied to displays such as color filters or liquid crystal displays.

Claims (15)

A colored composition containing a compound represented by formula (I) and a resin,

In formula (I), L ¹ represents -CO- or -SO ₂ -; R ¹ to R ⁵ and R ¹² to R ¹³ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, the number of carbon atoms that may have a substituent 1 Hydrocarbyl groups up to 40 or heterocyclic groups that may have substituents; R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ , which may be bonded to each other to form a ring; R ¹¹ and R ¹⁰¹ , each independently represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group, except that R ¹¹ is

, -NHC ₃ H ₇ , -NHMe, ethoxy group, phenoxy group, methyl group or tolyl group; R ¹⁰² , represents a hydrogen atom, a hydrocarbon group of 1 to 40 carbons that may have a substituent, or may be substituted M represents a hydrogen atom or an alkali metal atom; when there are plural R ¹⁰¹ , R ¹⁰² and M, they may be the same or different; the wavy line represents the E body or the Z body. The colored composition described in item 1 of the scope of patent application, wherein the compound represented by formula (I) is a compound represented by formula (Ia),

In formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and wavy lines indicate the same meaning as the first item in the scope of the patent application; L ² , means -CO- or -SO ₂ -; R ¹⁴ , Represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. The coloring composition described in item 2 of the scope of patent application, wherein R ¹¹ and R ¹⁴ are the same group, and L ¹ and L ² are the same group. The coloring composition as described in item 2 of the scope of patent application, wherein R ¹¹ and R ¹⁴ are each independently an optionally substituted alkyl group having 1 to 40 carbon atoms, optionally substituted phenyl group, optionally substituted The naphthyl group which may have a substituent, the tetrahydronaphthyl group which may have a substituent, the thienyl group which may have a substituent, the furyl group which may have a substituent, or the pyridyl group which may have a substituent. The coloring composition as described in item 3 of the scope of the patent application, wherein R ¹¹ and R ¹⁴ are each independently an optionally substituted alkyl group having 1 to 40 carbon atoms, optionally substituted phenyl group, optionally substituted The naphthyl group which may have a substituent, the tetrahydronaphthyl group which may have a substituent, the thienyl group which may have a substituent, the furyl group which may have a substituent, or the pyridyl group which may have a substituent. The coloring composition described in item 1 of the scope of patent application, wherein the compound represented by formula (I) is a compound represented by formula (Ib),

In formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line indicate the same meaning as the first item in the scope of the patent application; R ²⁰ and R ³⁰ are bonded to form ring Q; ring Q may be A ring with substituents and ring members with a number of 5 to 7, the ring Q may be a hydrocarbon ring or a heterocyclic ring; in the ring Q, the number of members that can be bonded to a ring selected from a hydrocarbon ring and a heterocyclic ring is A single ring of 5 to 7 or a condensed ring of the single ring. The coloring composition described in item 6 of the scope of patent application, wherein the compound represented by formula (I) is a compound represented by formula (Ic),

In formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the wavy line indicate the same meaning as the first item in the scope of patent application; R ⁶ and R ⁷ each independently represent a hydrogen atom, -CO- R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, can The substituted hydrocarbon group having 1 to 40 carbon atoms or the optionally substituted heterocyclic group; R ¹⁰¹ , R ¹⁰² and M have the same meaning as described above. The coloring composition according to any one of items 1 to 7 in the scope of patent application, wherein R ¹ is a hydrogen atom, and R ² to R ⁵ are each independently a hydrogen atom or a nitro group. A coloring and curable resin composition comprising the coloring composition described in any one of items 1 to 8 in the scope of patent application, a polymerizable compound and a polymerization initiator. A color filter, which is formed of the colored hardening resin composition described in item 9 of the scope of patent application. A liquid crystal display, which contains the color filter described in item 10 of the scope of patent application. A compound represented by formula (II);

In the formula (II), R ¹ to R ⁵ and R ¹² to R ¹³ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group with 1 to 40 carbon atoms or optionally substituted heterocyclic group; R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring; R ¹¹ and R ¹⁰¹ each independently represent a carbon that may have a substituent A hydrocarbon group having a number of 1 to 40 or a heterocyclic group which may have a substituent, except that R ¹¹ is

, -NHC ₃ H ₇ , -NHMe, ethoxy, phenoxy, methyl or tolyl; R ¹⁰² represents a hydrogen atom, a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent or may be substituted M represents a hydrogen atom or an alkali metal atom; when there are plural R ¹⁰¹ , R ¹⁰² and M, they may be the same or different; the wavy line represents the E body or the Z body. A compound represented by formula (II-a1),

In the formula, R ¹ to R ⁵ and R ¹² to R ¹³ each independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON (R ¹⁰² ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent; R ¹⁰¹ , It represents a hydrocarbon group with 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent; R ¹⁰² represents a hydrogen atom, a hydrocarbon group with 1 to 40 carbon atoms which may have a substituent, or a substituted group Heterocyclic group; R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ , which may be bonded to each other to form a ring; R ¹¹¹ , represents a heterocyclic group which may have a substituent Or may have a substituted hydrocarbon group of 1 to 40 carbons, but excluding R ¹¹¹ is

, -NHC ₃ H ₇ , -NHMe, ethoxy, phenoxy, methyl or tolyl; however, R ¹¹¹ is a hydrocarbon group with 1 to 40 carbons that may have a substituent, and R ¹² and R ¹³ When either one is -SO ₂ -R ¹¹¹ , and the other of R ¹² and R ¹³ is a cyano group, at least one of R ² to R ⁵ represents -CO-R ¹⁰² , -COO-R ¹⁰¹ ,- OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO -N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, the number of carbon atoms that may have substituents is from 1 to 40 Hydrocarbyl group or heterocyclic group which may have substituents; M represents a hydrogen atom or an alkali metal atom; when there are plural R ¹⁰¹ , R ¹⁰² and M, these may be the same or different; wavy line represents E Body or Z body. The compound described in item 13 of the scope of patent application, wherein R ¹¹¹ is a heterocyclic ring which may have a substituent. A compound represented by formula (Ib);

In formula (Ib), L ¹ represents -CO- or -SO ₂ -; R ²⁰ and R ³⁰ are bonded to form ring Q; ring Q may have substituents, and the number of ring members is 5 to A ring of 7, the ring Q may be a hydrocarbon ring or a heterocyclic ring; in the ring Q, a monocyclic ring of 5 to 7 members can be bonded to a ring selected from a hydrocarbon ring and a heterocyclic ring or the monocyclic condensation Synthetic ring; R ¹ to R ⁵ , each independently represents a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) _2. Halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, optionally substituted hydrocarbon group with 1 to 40 carbon atoms or optionally substituted heterocyclic group; R ² and R ³ , R ³ and R ⁴ and R ⁴ and R ⁵ may be bonded to each other to form a ring; R ¹¹ and R ¹⁰¹ each independently represent a substituted hydrocarbon group having 1 to 40 carbon atoms or a substituted heterocyclic group Cyclic group, except that R ¹¹ is excluded

, -NHC ₃ H ₇ , -NHMe, ethoxy, phenoxy, methyl or tolyl; R ¹⁰² represents a hydrogen atom, a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent or may be substituted M represents a hydrogen atom or an alkali metal atom; when there are plural R ¹⁰¹ , R ¹⁰² and M, they may be the same or different; the wavy line represents the E body or the Z body.