JP2013116974A - Quinophthalone compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a quinophthalone compound excellent in solvent solubility and high in color purity.SOLUTION: The quinophthalone compound is represented by formula (1) [wherein Ris a hydrogen atom, a 1-12C alkyl group which may be substituted with an optional substituent or the like; Rto Rare each independently a hydrogen atom, a halogen atom, or a straight-chain or branched-chain 1-8C alkyl group; Y and Z are each independently a hydrogen atom, -COORor -CON(R); at least one of Y and Z is -COOR; Ris a 1-12C alkyl group which may be substituted with an optional substituent, or -CH-CO-R(Ris a straight-chain or branched-chain 1-8C alkyl group or the like)].

Description

  The present invention relates to a quinophthalone compound. Specifically, the present invention relates to a quinophthalone compound having high transmittance at 490 nm and high solubility in an organic solvent.

  Dyes have long been used as dyes for dyeing various fibers. In recent years, ink sheets for inkjet inks, synthetic resin and dyes for synthetic fiber materials, colorants for polymer materials, and thermal transfer type image forming materials have been used. It is used in various fields such as toner for electrophotography, magnetic recording material, and optical recording material. For this reason, the development of dyes that combine these performances is desired, including the performance required of dyes, not only for color development but also for light resistance, heat resistance, solubility in solvents, and compatibility with resins. .

  A quinophthalone compound is a yellow pigment and is known as a pigment excellent in heat resistance, moisture resistance, and light resistance (see, for example, Patent Documents 1 and 2).

JP 59-43086 A Special table 2008-516006 gazette

  However, the quinophthalone compound described in Patent Document 1 has room for improvement in terms of color purity, and the quinophthalone compound described in Patent Document 2 is difficult to dissolve in a solvent, and it is difficult to dissolve in a solvent. It was difficult to apply. In particular, ink-jet inks include oil-based inks in which a dye is dissolved in a solvent. However, in such applications, high solubility in a solvent is required.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a quinophthalone compound having excellent solvent solubility and high color purity.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the following compounds. That is, the object of the present invention is to provide the following formula (1) or (2):

In the formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with any substituent, —CH ₂ —CO—R ₆ (R ₆ is 1 to 1 carbon atom) 8 linear or branched alkyl group), an acyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group optionally substituted with an arbitrary substituent, or silyl having 3 to 18 carbon atoms. R _{2 to} R ₅ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 8 carbon atoms,
Y and Z each independently represent a hydrogen atom, —COOR ₇ , or —CON (R ₈ ) ₂ , and at least one of Y and Z represents —COOR ₇ ;
Here, R ₇ is an alkyl group having 1 to 12 carbon atoms which may be substituted with an arbitrary substituent, —CH ₂ —CO—R ₉ (R ₉ is a straight chain or branched chain having 1 to 8 carbon atoms) Chain alkyl group), or the following formula:

In the above formula, R ₁₀ represents an alkylene group having 1 to 3 carbon atoms, R ₁₁ represents an alkyl group having 1 to 8 carbon atoms, and m is an integer of 1 to 4. R ₈ is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with any substituent, or the following formula:

In the above formula, R ₁₂ represents an alkylene group having 1 to 3 carbon atoms, R ₁₃ represents an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4. 2 R ₈ are not simultaneously hydrogen atoms,
In the formula (2), R _{1 ′} is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with any substituent, —CH ₂ —CO—R _{6 ′} (R _{6 ′} is a carbon atom) A linear or branched alkyl group having 1 to 8 carbon atoms), an acyl group having 1 to 10 carbon atoms, an allyl group, an optionally substituted phenyl group, or 3 to 3 carbon atoms. 18 represents a silyl group, R _{2 ′ to} R _{5 ′} each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 8 carbon atoms,
Y ′ and Z ′ each independently represent —COOR ₁₄ , —CH ₂ —CO—R ₁₅ , or —CON (R ₁₆ ) ₂ ;
Here, R ₁₄ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with any substituent, or the following formula:

In the above formula, R ₁₇ represents an alkylene group having 1 to 3 carbon atoms, R ₁₈ represents an alkyl group having 1 to 8 carbon atoms, and l is an integer of 1 to 4. R ₁₅ represents a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₁₆ is independently a hydrogen atom or an optionally substituted carbon atom having 1 to 1 carbon atoms. 12 alkyl groups or the following formula:

In the above formula, R ₁₉ represents an alkylene group having 1 to 3 carbon atoms, R ₂₀ represents an alkyl group having 1 to 8 carbon atoms, and k is an integer of 1 to 4. 2 R ₁₆ do not simultaneously become a hydrogen atom,
When one of Y ′ and Z ′ is —COOH, the other is —CON (R ₁₆ ) ₂ , and X represents an arbitrary divalent linking group; The

  The quinophthalone compound of the present invention has a high transmittance at 490 nm, that is, the color has almost no redness and is close to pure yellow, that is, has a high color purity. In addition, since the gram extinction coefficient (absorbance per gram) is high, a strong yellow color can be obtained even if a coloring power is high, that is, a relatively small amount of yellow pigment is used. Moreover, since it has a maximum absorption wavelength in the range of 430 nm to 470 nm, the high color purity and the high coloring power are in a practical balance. In addition, the quinophthalone compound of the present invention has high solvent solubility in cyclohexanone or N-methylpyrrolidone.

It is a figure which shows the absorption spectrum of a compound (B). It is a figure which shows the absorption spectrum of a compound (A). It is a figure which shows the absorption spectrum of a compound (E). It is a figure which shows the absorption spectrum of a compound (G).

  Hereinafter, the present invention will be described in detail.

  The quinophthalone compound represented by the formula (1) or (2) has the following common structure.

In the above _formula, R 1 to R ₅ are the same as _R 1 to R ₅ of formula (1), corresponding to R _{1 'to} R _5' of formula (2).

  The compounds represented by the formula (1) or (2) have a common structure in which the 3'-position is a hydrogen atom and the oxygen atom is present at the 8'-position. The compound disclosed in Patent Document 1 has a hydroxy group at the 3 'position and a hydrogen atom bonded to the 8' position. Due to the difference in structure, the compound represented by the formula (1) or (2) has a sharp absorption wavelength spectrum, a high gram extinction coefficient, and a high transmittance at 490 nm. It is presumed that (improved color development) could be realized. The quinophthalone compound represented by the formula (1) or (2) has high color developability and exhibits a bright bluish yellow.

Further, in the compound disclosed in Patent Document 2, at least one of the substituents at the 4 to 7 position is a carboxyl group, whereas the compound represented by the formula (1) of the present application is substituted at the 4 to 7 position. As a group, one or two —COOR ₇ are introduced. By introducing such a substituent, the lipophilicity of the whole compound is improved, and it is presumed that the solubility in an organic solvent is improved. Similarly, for the compound represented by the formula (2), the presence or absence of one or two of —COOR ₁₄ , —CH ₂ —CO—R ₁₅ , or —CON (R ₁₆ ) ₂ increases the lipophilicity of the entire compound. It is estimated that the solubility in the organic solvent is improved.

  Next, the compounds represented by formulas (1) and (2) will be specifically described.

In Formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may be substituted with any substituent, —CH ₂ —CO—R ₆ (R ₆ is 1 to 8 carbon atoms). A linear or branched alkyl group), an acyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group which may be substituted with any substituent, or a silyl group having 3 to 18 carbon atoms. Represent.

  In the present specification, the alkyl group includes any of straight chain, branched chain, and cyclic unless otherwise specified.

The alkyl group in R ₁ is an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl Group, neopentyl group, 1,2-dimethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, cycloheptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group And dodecyl group.

The alkyl group in R ₆ is a linear or branched alkyl group having 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1, 2-dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl- Examples include 1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group and the like.

Examples of the acyl group for R ₁ include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, a benzoyl group, and a pt-butylbenzoyl group.

The silyl group in R ₁ is a group representing —Si (R) ₃ (R is each independently an alkyl group or aryl group having 1 to 8 carbon atoms). More specifically, a trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl group, methyldiphenylsilyl group, t-butyldiphenylsilyl group and the like can be mentioned.

The substituent optionally present in the alkyl group or the phenyl group is not particularly limited, and examples thereof include a halogen atom, a nitro group, a cyano group, an alkoxy group, a heterocyclic group, an aryl group, and a hydroxy group. , Acyl group, alkyl group, phenyl group, halogenated alkyl group, halogenated alkoxyl group, amino group, alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylamino Examples thereof include, but are not limited to, a carbonyl group, an alkoxysulfonyl group, an alkylthio group, a carbamoyl group, an aryloxycarbonyl group, and an oxyalkyl ether group. When a plurality of these substituents are present, they may be the same or different. Some of the above substituents are shown below with more specific examples. In addition, the substituent which exists depending on the case is not the same as R ₁ to be substituted. For example, when R ₁ is an alkyl group, it is not further substituted with an alkyl group.

  First, among the substituents optionally present in the above alkyl group or phenyl group, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably chlorine. Is an atom.

  Among the substituents optionally present in the alkyl group or the phenyl group, examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, Examples thereof include linear, branched or cyclic alkoxy groups such as isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, and octyloxy group.

  Among the substituents optionally present in the alkyl group or the phenyl group, the heterocyclic group has 2 to 10 carbon atoms and is at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom A heterocyclic group containing, and not limited to a monocyclic heterocyclic group, a condensed heterocyclic group in which a plurality of heterocyclic rings are condensed, a heterocyclic ring and a hydrocarbon ring (non-aromatic hydrocarbon ring or aromatic hydrocarbon) And a condensed heterocyclic group obtained by condensation (ortho condensation, ortho-and-peri condensation, etc.). The heterocyclic group may be non-aromatic or aromatic. Furthermore, in the condensed heterocyclic group in which the heterocyclic ring and the hydrocarbon ring are condensed, either the heterocyclic ring or the hydrocarbon ring may have a bond. As the heterocyclic group having a nitrogen atom as a hetero atom, a 5-membered or 6-membered monocyclic heterocyclic group such as a pyrrolyl group, an imidazolyl group, a pyridyl group, a pyrazinyl group, an indolyl group, a quinolyl group, an isoquinolyl group, a quinazolyl group, Examples thereof include a condensed heterocyclic group in which a 5-membered or 6-membered heterocyclic ring such as a carbazolyl group, a carbolinyl group, a phenanthridinyl group, an acridinyl group, or a phenazinyl group is condensed with a hydrocarbon ring. As the cyclic group, a 5-membered or 6-membered monocyclic heterocyclic group such as a furyl group (for example, a tetrahydrofurfuryl group), a 5-membered or 6-membered heterocyclic ring such as an isobenzofuranyl group or a chromenyl group is a hydrocarbon ring. Examples thereof include a condensed heterocyclic group condensed with the above. The heterocyclic group having a sulfur atom as a hetero atom includes a condensed heterocyclic ring in which a 5- or 6-membered monocyclic heterocyclic group such as a thienyl group or a 5- or 6-membered heterocyclic ring such as a thiantenyl group is condensed to a hydrocarbon ring Group etc. are included. In addition, examples of the heterocyclic group having different heteroatoms include 5-membered or 6-membered monocyclic groups such as morpholinyl group, isothiazolyl group and isoxazolyl group, and 5-membered or 6-membered heterocyclic rings such as phenoxathiinyl group. And a condensed heterocyclic group in which is condensed to a hydrocarbon ring. Preferred heterocyclic groups include 5- or 6-membered heterocyclic groups having at least a nitrogen atom as a hetero atom (pyrrolyl, pyridyl, etc.), 5- or 6-membered heterocyclic groups having at least a nitrogen atom as a hetero atom, and aromatic carbonization A heterocyclic group condensed with hydrogens (for example, a carbazolyl group) and the like are included. Of these, when considering particularly heat resistance such as heat resistance and solubility in an organic solvent, specifically, a tetrahydrofurfuryl group, a 4-picolyl group, and the like are preferable.

  Of the substituents optionally present in the alkyl group or phenyl group, examples of the aryl group include a phenyl group and a naphthyl group.

  Examples of the acyl group include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, a benzoyl group, and a pt-butylbenzoyl group. Among these, acetyl, An ethylcarbonyl group is preferred.

  The alkyl group is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethyl Butyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n -An octyl group, 2-ethylhexyl group, etc. are mentioned. Of these, a methyl group and an ethyl group are preferred.

  The halogenated alkyl group is a group in which a part of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms is halogenated, and is a chloromethyl group. Bromomethyl group, trifluoromethyl group, chloroethyl group, 2,2,2-trichloroethyl group, bromoethyl group, chloropropyl group, bromopropyl group and the like.

  The halogenated alkoxyl group is a group in which a part of a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms is halogenated, and is a chloromethoxy group. Bromomethoxy group, trifluoromethoxy group, chloroethoxy group, 2,2,2-trichloroethoxy group, bromoethoxy group, chloropropoxy group, bromopropoxy group and the like.

  The alkylamino group is an alkylamino group having an alkyl moiety having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and includes a methylamino group, ethylamino group, n-propylamino group, n- A butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group and the like can be mentioned. Of these, a methylamino group, an ethylamino group, an n-propylamino group, and an n-butylamino group are preferable.

  Examples of the alkylcarbonylamino group include acetylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, iso-propylcarbonylamino group, n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group. , T-butylcarbonylamino group, n-pentylcarbonylamino group, n-hexylcarbonylamino group, cyclohexylcarbonylamino group, n-heptylcarbonylamino group, 3-heptylcarbonylamino group, n-octylcarbonylamino group and the like. It is done.

  Examples of the arylamino group include phenylamino group, p-methylphenylamino group, pt-butylphenylamino group, diphenylamino group, di-p-methylphenylamino group, di-pt-butylphenylamino group, and the like. Is mentioned.

  As arylcarbonylamino group, benzoylamino group, p-chlorobenzoylamino group, p-methoxybenzoylamino group, pt-butylbenzoylamino group, p-trifluoromethylbenzoylamino group, m-trifluoromethylbenzoylamino Groups and the like.

  The alkoxycarbonyl group is a C 1-8 carbon atom which may contain a hetero atom in the alkyl group part of the alkoxyl group, preferably 1-5 alkoxycarbonyl, or a C 3-8 carbon atom which may contain a hetero atom. , Preferably 5 to 8 cyclic alkoxycarbonyl. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, and a tert-butoxycarbonyl group. . Of these, a methoxycarbonyl group and an ethoxycarbonyl group are preferred.

  Examples of the alkylaminocarbonyl group include a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an n-butylaminocarbonyl group, a sec-butylaminocarbonyl group, an n-pentylaminocarbonyl group, and an n-hexylaminocarbonyl group. Group, n-heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, Examples include di-sec-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-heptylaminocarbonyl group, di-n-octylaminocarbonyl group, and the like. That.

  Examples of the alkoxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group.

Examples of the alkylthio group include a methylthiophenyl group, an ethylthiophenyl group, a t-butylthiophenyl group, a di-tert-butylthiophenyl group, a 2-methyl-1-ethylthiophenyl group, and a 2-butyl-1-methylthiophenyl group. Etc.

  The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 30 carbon atoms. For example, a 2-methylphenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2,6-dimethylphenyloxycarbonyl group, 2, 4,6-trimethylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 2,2-ethylhexylphenyloxycarbonyl Group, 3- (2-ethylhexyloxy) phenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-chlorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-butoxy E alkenyloxy group and the like.

  Examples of the oxyalkyl ether group include ethylene glycol heptyl ether, oxyethylene oleyl ether, oxypropylene butyl ether, and oxypropylene 2-ethylhexyl ether.

In formula (1), R _{2 to} R ₅ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 8 carbon atoms. Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include those described in the above R ₆ column. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R _{2 to} R ₅ are preferably hydrogen atoms in terms of coloring power.

In formula (1), Y and Z each independently represent a hydrogen atom, —COOR ₇ , or —CON (R ₈ ) ₂ . From the viewpoint of solvent solubility, at least one of Y and Z represents —COOR ₇ .

Specific examples of the alkyl group having 1 to 12 carbon atoms represented by R ₇ and R ₈ include those described in the above R ₁ column. Moreover, if also substituents present in the alkyl group by, include those described in the section of the R _1.

Or R ₇ is

R ₈ is represented by

It is represented by Examples of the alkylene group having 1 to 3 carbon atoms represented by R ₁₀ and R ₁₂ include a methylene group, an ethylene group, a methylmethylene group, a propylene group, a dimethylmethylene group, and a methylethylene group. Specific examples of the alkyl group having 1 to 8 carbon atoms represented by R ₁₁ and R ₁₃ include those described in the above R ₆ column. m and n represent the number of repeating units of the oxyalkylene group (R ₁₀ O, R ₁₂ O) and are integers of 1 to 4. In consideration of coloring power and solvent solubility, m and n are preferably 1 or 2.

Although there are two R ₈ bonded to the nitrogen atom, R ₈ is not simultaneously a hydrogen atom from the viewpoint of solvent solubility. Two R _{8 s} may be the same or different from each other, but are preferably the same substituent from the viewpoint of symmetry.

R ₇ may be represented by —CH ₂ —CO—R ₉ (R ₉ is a linear or branched alkyl group having 1 to 8 carbon atoms). Here, specific examples of the alkyl group represented by R ₉ include those described in the above R ₆ column.

The substituents representing R _{1 ′ to} R _{5 ′} in Formula (2) correspond to R _{1 to} R ₅ in Formula (1), respectively, and details and specific examples thereof are described in the columns of R _{1 to} R ₅ above. This is the same as described in.

In formula (2), Y ′ and Z ′ each independently represent —COOR ₁₄ , —CH ₂ —CO—R ₁₅ , or —CON (R ₁₆ ) ₂ .

Here, specific examples of the alkyl group having 1 to 12 carbon atoms represented by R ₁₄ and R ₁₆ include those described in the column of R ₁ above. Moreover, if also substituents present in the alkyl group by, include those described in the section of the R _1.

R ₁₄ is

In which R ₁₆ is

The substituent represented by these is also shown. Specific examples of the alkylene group having 1 to 3 carbon atoms represented by R ₁₇ and R ₁₉ include those described in the above R ₁₀ and R ₁₂ columns. Specific examples of the alkyl group having 1 to 8 carbon atoms represented by R ₁₈ and R ₂₀ include those described in the above R ₆ column. l and k represent the number of repeating units of the oxyalkylene group (R ₁₇ O, R ₁₉ O) and are integers of 1 to 4. In consideration of coloring power and solvent solubility, l and k are preferably 1 or 2.

R ₁₄ is an alkyl group, or from the viewpoint of solvent solubility,

It is preferable that it is a substituent represented by these.

R ₁₆ is an alkyl group from the viewpoint of solvent solubility, or

It is preferable that it is a substituent represented by these.

R ₁₆ may represent a hydrogen atom, but from the viewpoint of solvent solubility, two R ₁₆ do not simultaneously become a hydrogen atom. The two R ₁₆ may be the same or different from each other, but are preferably the same substituent from the viewpoint of symmetry.

R ₁₅ represents a linear or branched chain having 1 to 8 carbon atoms. Specific examples include those described in the above R ₆ column.

In addition, when either one of Y ′ and Z ′ is —COOH, the other is —CON (R ₁₆ ) ₂ from the viewpoint of solvent solubility.

Examples of the divalent linking group represented by X include —O—, —SO—, —SO ₂ —, —CO—, —CR ₂₁ R ₂₂ — (R ₂₁ and R ₂₂ are each independently a halogen atom. atom (preferably fluorine atom) represents an alkyl group having 1 to 4 carbon atoms which may straight or branched chain optionally substituted by _{a), - CH 2 -CH 2 -} , - S -, - CO-O-, —O—CO—O—, —C (═S) —O—, —O—C (═S) —O—, —CO—NR ₂₃ — (R ₂₃ is a hydrogen atom or a straight or branched chain. represents an alkyl group having 1 to 4 carbon _{atoms), - O-CH 2 -} , - S-CH 2 -, - NR 23 -, - CR 21 = CR 22 - , and the like. Among these, in terms of solvent solubility, the divalent linking group representing X is preferably —O—, —SO—, —SO ₂ —, —CO—, or —CR ₂₁ R ₂₂ —, -Is more preferable.

  From the viewpoint of solvent solubility, the compound represented by the formula (1) is represented by the following formula (3) or (4):

It is preferable that it is a compound represented by these.

  Note that the compounds represented by the above formula (3) or (4) are in a tautomeric relationship with each other, and when a compound is represented by one chemical formula in this specification, it is represented by the other chemical formula. The compound is also included.

  Similarly, from the viewpoint of solvent solubility, the compound represented by the formula (2) is represented by the following formula (5) or (6):

It is preferable that it is a compound represented by these.

The total number of carbon atoms present in R ₁ , R ₇ and R ₈ ; or R _{1 ′} , R _14, R ₁₅ and R ₁₆ ; is preferably 8 or more. In consideration of solubility in cyclohexanone and coloring power, the total number of carbon atoms is preferably 11 or more, more preferably 11 or more and 60 or less, and further preferably 14 or more and 48 or less. It is presumed that the presence of more than a certain number of carbon atoms in the compound increases the lipophilicity of the compound and increases the solvent solubility. The total number of carbon atoms present in R ₁ , R ₇ and R ₈ ; or R _{1 ′} , R ₁₄ , R ₁₅ and R ₁₆ ; is preferably as large as possible from the viewpoint of solubility, but from the viewpoint of coloring power. Is preferably as small as possible.

  The compounds of formulas (1) and (2) each have tautomers having a plurality of structures, and these tautomers are also within the scope of the present invention.

  As a suitable embodiment of the compound represented by Formula (1), the following compounds are illustrated.

  As a suitable embodiment of the compound represented by Formula (2), the following compounds are illustrated.

  The above preferred embodiment is the same for the quinophthalone compounds represented by formulas (3) and (4), which are preferred forms of the quinophthalone compound represented by formula (1). Moreover, the said preferable embodiment is the same also in the quinophthalone compound represented by Formula (5) and (6) which is a suitable form of the quinophthalone compound represented by Formula (2).

  The method for producing the quinophthalone compound of the present invention is not particularly limited, and a conventionally known method can be appropriately used. Hereinafter, an embodiment of a method for producing a quinophthalone compound will be described.

  First, an 8-alkyloxyquinaldine derivative represented by the following formula (I) (hereinafter, also simply referred to as “quinaldine derivative”);

And pyromellitic anhydride are reacted to form the following formula (II):

Is obtained. In the formulas (I) and (II), R _{1 to} R ₅ are defined by the structure of the desired quinophthalone compound. Specifically, these definitions are the same as those of the compound represented by the formula (1). Therefore, the description is omitted here.

  At this time, the reaction molar ratio between the quinalzine derivative and pyromellitic acid anhydride is appropriately set depending on the compound, but is usually quinaldine derivative: pyromellitic acid anhydride = 1: 1 to 1.5.

  The above reaction may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. Examples of the solvent used at this time include benzoic acid, benzonitrile, tetralin, nitrobenzene, 1,2,4-trichlorobenzene, sulfolane and the like. The amount of the solvent used is appropriately adjusted depending on the reaction, but is such an amount that the total concentration of the quinaldine derivative and pyromellitic anhydride is usually 10 to 50% by mass.

  In addition, the reaction conditions between the quinaldine derivative and pyromellitic acid anhydride are not particularly limited as long as both proceed to obtain a compound represented by the formula (II). Specifically, the reaction temperature is usually 140 to 240 ° C., preferably 150 to 210 ° C., and the reaction time is usually about 1 to 50 hours, preferably 1.5 to 24 hours.

Subsequently, the compound represented by the formula (II) and R ₇ —OH, and sometimes NH (R ₈ ) ₂ (R ₇ —OH, and NH (R ₈ ) ₂ are also simply referred to as “reaction precursor”. ) Can be reacted to obtain a compound represented by the formula (3) or (4). Here, R ₇ and R ₈ are defined by the structure of the desired quinophthalone compound. Specifically, these definitions are the same as those of the compound represented by the formula (1). Omitted.

The reaction between the compound represented by the formula (II) and the reaction precursor can be carried out using various conventionally known reactions such as a method via an acid chloride, a Fischer ester synthesis reaction using an acid catalyst, and the like. However, for example, an acid-catalyzed Fischer ester synthesis reaction can be used. At this time, in order to advance the esterification reaction, it is preferable to heat and reflux while dehydrating. As a dehydration method, a conventionally known method can be used. For example, water generated using a Dean-Stark trap or the like can be removed from the reaction system. The acid catalyst used is not particularly limited, and a conventionally known catalyst can be used. For example, p-toluenesulfonic acid monohydrate, concentrated sulfuric acid, trifluoroacetic acid and the like can be used.

  The reaction molar ratio between the compound represented by the formula (II) and the reaction precursor is appropriately set depending on the desired compound.

  The reaction between the compound represented by the formula (II) and the reaction precursor is preferably performed in an organic solvent. The solvent used at this time is not particularly limited, but benzene, toluene, xylene, and in some cases, a reaction precursor can be used. Although the usage-amount of a solvent is suitably adjusted with reaction, it is an quantity that the sum total density | concentration with the compound represented by Formula (II) and a reaction precursor will be 1-50 mass% normally.

  In addition, the reaction conditions for the compound represented by the formula (II) and the reaction precursor are not particularly limited as long as both proceed to obtain the compound represented by the formula (II). Specifically, the reaction temperature is usually 70 to 180 ° C., preferably 80 to 170 ° C., and the reaction time is usually about 1 to 72 hours, preferably 0.5 to 48 hours.

  After the reaction, filtration, washing and drying may be performed according to a conventionally known method. By such an operation, the quinophthalone compound can be obtained efficiently and with high purity.

  In the above, pyromellitic anhydride was used as an example, but instead of pyromellitic anhydride, trimellitic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-sulfonyldiphthalic anhydride A desired quinophthalone compound can be produced by appropriately using a conventionally known synthesis method using a product.

  Since the quinophthalone compound of the present invention as described above has a maximum absorption wavelength in the range of 430 to 470 nm, it can be used as a yellow dye (yellow dye compound). In addition, the maximum absorption wavelength (λmax) of the absorption spectrum of the above quinophthalone compound means a value measured in cyclohexanone using an ultraviolet-visible spectrophotometer.

  The quinophthalone compound of the present invention is soluble (compatible) with a solvent, particularly cyclohexanone (CHN) or N-methylpyrrolidone (NMP), acetone, dimethylformamide, dimethyl sulfoxide, chloroform, toluene, ethyl acetate, tetrahydrofuran and the like. More preferably, and excellent solubility (compatibility) with cyclohexanone and N-methylpyrrolidone. The solvent solubility of the quinophthalone compound of the present invention is not particularly limited, and the higher the better. For example, the concentration of the quinophthalone compound relative to the amount of CHN necessary to dissolve the quinophthalone compound of the present invention is preferably 1% by weight or more, more preferably 5% by weight or more, and more preferably 10% by weight or more. More preferably it is. Further, the concentration of the quinophthalone compound with respect to the amount of NMP necessary for dissolving the quinophthalone compound of the present invention is preferably 10% by weight or more, and more preferably 20% by weight or more.

  Thus, since the quinophthalone compound of the present invention is excellent in heat resistance and solvent solubility, it can be suitably used in various applications, particularly ink jet inks.

  Hereinafter, as an application of the quinophthalone compound of the present invention, an inkjet ink will be described as an example. That is, another embodiment of the present invention is an inkjet ink containing the quinophthalone compound of the present invention.

  The inkjet ink of the present invention is the same as the conventional inkjet, such as JP 2010-195904 A, JP 2009-132812 A and JP 11-106693 A, except that it contains the quinophthalone compound of the present invention as a pigment. Can be an ink.

  The composition of the inkjet ink of the present invention can be the same as a known composition except that it contains the quinophthalone compound of the present invention as a pigment. For example, the inkjet ink of the present invention contains a pigment, a resin, and a solvent.

  The inkjet ink of the present invention must contain the quinophthalone compound of the present invention as a pigment. Here, the blending amount of the quinophthalone compound of the present invention is not particularly limited, but is preferably 1 to 50% by weight, more preferably 3 to 30% by weight based on the total weight of the ink. Within such a range, a printed surface with a sufficient density can be obtained, and a stable dissolved state in ink can be obtained. In addition, the quinophthalone compound of the present invention may be used alone or in the form of a mixture of two or more.

  In addition, the inkjet ink of the present invention may be used in combination with other pigments or dyes. Other pigments or dyes are not particularly limited, and known pigments or dyes can be used. The other pigments or dyes may be used alone or in the form of a mixture of two or more.

  The resin used in the inkjet ink of the present invention is not particularly limited, and a known resin used in the inkjet ink can be used. The resin can be appropriately selected in consideration of properties such as viscosity and adhesion. Specific examples include vinyl chloride-vinyl acetate copolymer, acrylic resin, butyral resin, polyamide resin, nitrocellulose, phenol resin, xylene resin, maleic acid resin, and silicon resin. The weight average molecular weight of the resin is not particularly limited and can be appropriately selected in consideration of a desired ink viscosity and the like. Specifically, the weight average molecular weight of the resin is preferably 1000 to 40000. Within such a range, the viscosity of the ink can be adjusted to an appropriate level. Further, the blending amount of the resin (resin content of the ink) is not particularly limited, but is preferably 0.5 to 20% by weight, and more preferably 0.6 to 15% by weight with respect to the total weight of the ink. In such a range, an appropriate ink viscosity can be obtained, so that ink can be stably ejected without causing droplet ejection or direction disturbance, and adhesion to a printing medium without peeling from the printing surface. And the dye can be retained well. In addition, the said resin may be used independently or may be used with the form of a 2 or more types of mixture. Further, for the purpose of further improving properties such as viscosity and adhesion, a higher molecular weight resin may be used in combination.

  The solvent used in the inkjet ink of the present invention is not particularly limited as long as it can dissolve other components (pigment, resin, etc.). Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, DIBK (diisobutyl ketone), cyclohexanone, N-methylpyrrolidone, DAA (diacetone alcohol); methanol, ethanol, isopropyl alcohol, butanol Alcohol solvents such as ethylene glycol monoethyl alcohol, ethylene glycol monomethyl alcohol and other alkylene glycol ether solvents; toluene, xylene and other hydrocarbon solvents; ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Examples thereof include ester solvents such as acetate. Of these, ketone solvents are preferable, and acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, and N-methylpyrrolidone are more preferable. The amount of the solvent is not particularly limited, but is preferably 0.1 to 20% by weight with respect to the total weight of the ink. If it is such a range, other components (a pigment | dye, resin, etc.) can be melt | dissolved efficiently. In addition, the said solvent may be used independently or may be used with the form of a 2 or more types of mixture.

  The ink-jet ink of the present invention may contain other additives. Here, the other additives are not particularly limited, and the additives used for the ink jet ink can be used in the same manner. For example, a conductivity adjusting agent, an amine, a dispersing agent, a polymerization inhibitor, a surface adjusting agent, a leveling agent, an ultraviolet absorber, and an antioxidant for increasing printing suitability and printed matter resistance.

  Of these, the conductivity adjusting agent is particularly effective when the ink of the present invention is used for high-speed printing by a continuous type ink jet printer. Here, it does not restrict | limit especially as an electrical conductivity regulator, A well-known electrical conductivity regulator can be used. Specific examples include potassium iodide, ammonium thiocyanate, potassium thiocyanate, and lithium nitrate. These conductivity adjusting agents are preferred because they do not show discoloration due to heat due to the residue on the printing surface. The blending amount of the conductivity adjusting agent is not particularly limited, but is preferably 0.1 to 2% by weight based on the total weight of the ink. In such a range, sufficient conductivity can be obtained, so that moderate charge deflection can be obtained, and no discoloration is induced. In addition, the said electrical conductivity modifier may be used independently or may be used with the form of 2 or more types of mixtures.

  The dispersant may be added for the purpose of improving the dispersibility of the dye and the storage stability of the ink composition. Here, it does not restrict | limit especially as a dispersing agent, A well-known dispersing agent can be used. Specifically, a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, a high Molecular copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl Examples include phenyl ether and stearylamine acetate. More specifically, styrene-acrylic acid copolymer, styrene-acrylic acid-alkyl acrylate ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid-acrylic acid alkyl ester copolymer, Salt: Styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, salts thereof; styrene-maleic acid half ester copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic Examples include acid copolymers, styrene-maleic anhydride-maleic acid half ester copolymers, salts thereof; benzyl methacrylate-methacrylic acid copolymers, salts thereof, and the like. The blending amount of the dispersant is not particularly limited, and can be appropriately set in consideration of desired dispersibility. Specifically, the blending amount of the dispersant is preferably 0.01 to 10% by weight with respect to the total weight of the ink. If it is such a range, components, such as a pigment | dye, can be disperse | distributed favorably. In addition, the said dispersing agent may be used independently or may be used with the form of 2 or more types of mixtures.

  The polymerization inhibitor can be added for the purpose of enhancing the storage stability of the ink and the stability in the recording apparatus. Here, it does not restrict | limit especially as a polymerization inhibitor, A well-known polymerization inhibitor can be used. Specific examples include hydroquinone, p-methoxyphenol, t-butylcatechol, and di-t-butylhydroxytoluene. The blending amount of the polymerization inhibitor is not particularly limited, and can be appropriately set in consideration of desired characteristics. Specifically, the blending amount of the polymerization inhibitor is preferably 0.01 to 5% by weight with respect to the total weight of the ink. If it is such a range, sclerosis | hardenability can be maintained and the storage stability of an ink can be improved. In addition, the said polymerization inhibitor may be used independently or may be used with the form of 2 or more types of mixtures.

  The inkjet ink of the present invention can be produced by a known method. For example, the ink-jet ink of the present invention can be prepared by adding a resin to a solvent, dissolving the mixture by stirring, and then adding a dye and other additives as necessary to sufficiently dissolve the resin. If necessary, the liquid mixture thus obtained may be filtered with a filter having a pore diameter of 3 μm or less, and further 1 μm or less.

  The usage form of the inkjet ink of the present invention is not particularly limited, and a known inkjet printing method can be applied. For example, the ink-jet ink of the present invention is supplied to a printer head of a printer for an ink-jet recording system, ejected from the printer head onto a substrate, and then irradiated with active energy rays such as ultraviolet rays and electron beams. Thereby, the ink on the printing medium is quickly cured. In addition, when irradiating an ultraviolet-ray as a light source of an active energy ray, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, LED, and sunlight can be used, for example. The light source is preferably selected appropriately according to the sensitivity of the polymerization initiator used. The ultraviolet intensity that can be used for curing the ink of the present invention is preferably 500 to 5,000 mW / cm 2 in a wavelength region effective for curing. Such irradiation intensity does not damage the recording medium and does not induce color fading.

  Due to the quinophthalone compound contained in the ink jet ink of the present invention, the printed matter develops a bright yellow color. Moreover, since the quinophthalone compound contained in the inkjet ink of the present invention is excellent in solvent solubility, a stable dissolved state can be maintained in the inkjet ink.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

Example 1 <Synthesis of Compound (A)>
A mixture of 118 g of benzoic acid and 37.7 g of pyromellitic anhydride was heated and dissolved at 180 ° C., and 25.0 g of 8-hydroxyquinaldine was added. After stirring at 180 ° C. for 2 hours, the mixture was washed with stirring with acetone and the precipitate was collected by filtration to obtain 57.2 g (101 mol%) of compound (a) as a red powder.

  3.00 g of the compound (a) was suspended in a mixed solution of 20 g of diethylene glycol monomethyl ether and 60 g of toluene, and 18.0 g of p-toluenesulfonic acid monohydrate was added. While dehydrating using a Dean-Stark trap, the mixture is heated to reflux for 33 hours. Water and ethyl acetate are added and insolubles are filtered off. After separation, the organic layer is washed with saturated brine and then dried over anhydrous sodium sulfate. did. After concentration, reprecipitation with ethyl acetate / hexane, the following compound (A):

As a yellow powder, 2.01 g (41 mol%) was obtained.

Example 2 <Synthesis of Compound (B)>
10.0 g of 8-hydroxyquinaldine was dissolved in 59 g of DMF, and 9.12 g of potassium carbonate and 15.5 g of 1-bromobutane were sequentially added. After stirring at 80 ° C. for 2.5 hours, the reaction solution was poured into 1M aqueous sodium hydroxide solution. The mixture was extracted with chloroform, washed with a saturated aqueous sodium hydrogen carbonate solution, and washed with saturated brine. The extract was dried over anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography (hexane / ethyl acetate = 85/15) to obtain 11.4 g (70 mol%) of the compound (b) as a colorless oily substance.

  A mixture of 34.0 g of benzoic acid and 10.1 g of pyromellitic anhydride was dissolved by heating at 180 ° C., and 10.0 g of compound (b) was added. The mixture was stirred at 190 ° C. for 3.5 hours and then washed with acetone, and the precipitate was collected by filtration to obtain 18.6 g (96 mol%) of compound (c).

  3.00 g of the compound (c) was suspended in a mixed solution of 19 g of isoamyl alcohol and 63 g of toluene, and 8.71 g of p-toluenesulfonic acid monohydrate was added. The mixture was heated under reflux for 2 hours while dehydrating using a Dean-Stark trap, and the reaction solution was poured into water. Insoluble matter was filtered off, and after separation, the aqueous layer was extracted with ethyl acetate, and the combined organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine. After drying over anhydrous sodium sulfate, the mixture was concentrated and hexane was added with stirring to precipitate a yellow powder. Filtered and the following compound (B):

As a yellow powder, 1.99 g (48 mol%) was obtained.

Example 3 <Synthesis of Compound (C)>
14.39 g of pyromellitic anhydride was dissolved in 85 g of nitrobenzene and 10.0 g of 8-hydroxyquinaldine was added to the mixture with heating and stirring at 180 ° C., followed by heating and stirring for 4 hours. After cooling to 100 ° C., 41.8 g of di (2-methoxyethyl) amine was added and allowed to stir for 2.5 hours. The mixture was cooled to room temperature, methanol was added, and the precipitate was collected by filtration to obtain 10.8 g (35 mol%) of compound (e) as a yellow powder.

  1.00 g of compound (d) was dissolved in 9.38 g of dimethylformamide, 0.25 g of sodium bicarbonate and 1.33 g of 1-chloropinacholine were added, and the mixture was stirred at 80 ° C. for 3.5 hours. The reaction solution was poured into 3.6 wt% hydrochloric acid, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. The inorganic component was filtered off, purified by silica gel column chromatography (chloroform / ethyl acetate = 9/1 → 3/2), and washed with methanol / water, whereby the following compound (C):

0.56 g (41%) was obtained as a yellow powder.

Example 4 <Synthesis of Compound (D)>
25.0 g of 8-hydroxyquinaldine was dissolved in 99 g of DMF, and 32.6 g of potassium carbonate and 21.6 g of 1-chloropinacholine were sequentially added. After stirring at 60 ° C. for 2.5 hours, the reaction solution was poured into 200 g of water with vigorous stirring. The precipitate was collected by filtration to obtain 39.1 g (97 mol%) of the compound (e) as a white powder.

  24.3 g of compound (d) and 18.1 g of trimellitic anhydride were suspended in 48.5 g of sulfolane and heated at 180 ° C. for 1.5 hours. The precipitate was collected by filtration with stirring with acetone to obtain 40.5 g (100 mol%) of the compound (f) as a yellow powder.

  3.00 g of compound (f) was suspended in 25 g of diethylene glycol monomethyl ether, and 6.04 g of p-toluenesulfonic acid monohydrate was added. The mixture was heated at 120 ° C. for 2 hours, and the reaction solution was poured into water. The precipitate was collected by filtration and the following compound (D):

As a yellow powder, 1.99 g (48 mol%) was obtained.

Example 5 <Synthesis of Compound (E)>
A mixture of 32.4 g of benzoic acid and 13.70 g of 4,4′-oxydiphthalic anhydride was heated and dissolved at 190 ° C., and 7.03 g of 8-hydroxyquinaldine was added in portions over 1 hour. The mixture was further stirred with heating for 5 hours and then washed with acetone, and the precipitate was collected by filtration to obtain 15.7 g (79 mol%) of the compound (g) as a yellow powder.

  3.00 g of the compound (g) was suspended in a mixed solution of 16 g of diethylene glycol monomethyl ether and 58 g of toluene, and 11.4 g of p-toluenesulfonic acid monohydrate was added. The mixture was heated to reflux for 3 hours while dehydrating using a Dean-Stark trap, and the reaction solution was poured into water. The mixture was extracted with methyl ethyl ketone, washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. Finally washed with hexane, the following compound (E):

Was obtained as a yellow powder (0.95 g, 21 mol%).

Example 6 <Synthesis of Compound (Fa) + (Fb)>
The compound (g) was suspended in 5 g of acetone, and 0.59 g of di (2-ethylhexyl) amine and 0.90 g of triethylamine were sequentially added. After stirring for 10 minutes, the reaction solution was poured into 100 g of 7.2 wt% hydrochloric acid. The precipitate is collected by filtration and purified by silica gel column chromatography (acetone / chloroform) to obtain the following compound (Fa) and compound (Fb):

Of 0.56 g as a yellow powder (yield: 37 mol%).

Comparative Example 1 <Synthesis of Compound (G)>
7.00 g of isatin is put into an aqueous solution of 14.7 g of potassium hydroxide / 14.7 g of water, and then 42.3 g of toluene, 0.20 g of tetraethylammonium bromide and 9.78 g of bromoacetone are added at 90 ° C. Stir for 1 hour. After separating and removing the toluene layer, acid precipitation was carried out by adding concentrated hydrochloric acid dropwise while cooling the aqueous layer with ice. The precipitate was collected by filtration and washed with isopropyl alcohol with stirring to obtain 7.92 g (82 mol%) of compound (h) as a white powder.

  A mixture of 6.13 g of pyromellitic anhydride and 20.6 g of benzoic acid was dissolved at 190 ° C., and 5.71 g of compound (h) was added in portions over 1 hour. After stirring with heating for 6 hours, the precipitate was collected by filtration with acetone, and 8.89 g (88 mol%) of Compound (i) was obtained.

  3.00 g of compound (i) was suspended in a mixed solution of 19 g of diethylene glycol monomethyl ether and 69 g of toluene, and 13.7 g of p-toluenesulfonic acid monohydrate was added. The mixture was heated to reflux for 3 hours while dehydrating using a Dean-Stark trap, and the reaction solution was poured into water. The mixture was extracted with ethyl acetate and washed successively with saturated sodium hydrogen carbonate and saturated brine. The resultant was dried over anhydrous sodium sulfate, filtered, and concentrated to obtain 4.40 g (95 mol%) of the following compound (G) as a red solid.

Comparative Example 2 <Synthesis of Compound (H)>
The following compound (G) was produced in the same manner as in the production method of Compound Example 1-2 of JP-A-2008-516006.

<Maximum absorption wavelength, Gram extinction coefficient measurement>
A cyclohexanone solution of 30 mg of the obtained quinophthalone compound was diluted to 50 mL in a volumetric flask to prepare a 0.6 g / L solution. Subsequently, 1 mL was taken out from the adjusted solution with a whole pipette, and diluted to 50 mL with cyclohexanone in a volumetric flask to prepare a 0.012 g / L solution. The 0.012 g / L solution thus prepared was placed in a 1 cm square hard glass cell, and the absorption spectrum was measured using a spectrophotometer (model number U-2910, manufactured by Hitachi High-Tech).

  Typically, the absorption spectrum of compound (B) is shown in FIG. 1, the absorption spectrum of compound (A) is shown in FIG. 2, the absorption spectrum of compound (D) is shown in FIG. 3, and the absorption spectrum of compound (F) is shown in FIG. Show.

From the absorption spectrum, maximum absorption wavelengths λ _max (1) and λ _max (2) were determined. When the absorbances corresponding to λ _max (1) and λ _max (2) are A (1) and A (2), respectively, the absorbance per gram at the maximum absorption wavelength (εg (1), εg (2)) Was calculated by the following formula.

  The transmittance% T (490 nm) at 490 nm was determined. These numerical values are shown in Table 1.

<Solubility test>
Take 30 mg of the obtained quinophthalone compound in a vial, add cyclohexanone (CHN) or N-methylpyrrolidone (NMP) at room temperature (20 ° C.), and the weight of the minimum amount of CHN or NMP necessary to dissolve the quinophthalone compound. Asked. The concentration (wt%) of the quinophthalone compound in the determined solvent weight was calculated and used as the solubility (solubility).

  The obtained results are shown in Table 1.

  The compounds of Examples 1 to 6 had high transmittance at 490 nm and high color purity. On the other hand, the compound of Comparative Example 1 has a maximum absorption wavelength in substantially the same region as that of the example, but because of the broad spectrum, the transmittance at 490 nm is low and the color purity is inferior to that of the example. It became. This is presumably due to the difference in substituents bonded to the 3'-position and the 8'-position in the compounds of Examples 1 to 6 and Comparative Example 1.

  Further, Comparative Example 2 hardly dissolved in cyclohexanone, and the compounds of Examples 1 to 6 all improved the solubility of cyclohexanone compared to Comparative Example 2. This is presumed to be due to the difference in the substituents of Y and Z or Y ′ and Z ′ in the compounds of Examples 1 to 6 and Comparative Example 2.

Claims (3)

The following formula (1) or (2);

In the formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with any substituent, —CH ₂ —CO—R ₆ (R ₆ is 1 to 1 carbon atom) 8 linear or branched alkyl group), an acyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group optionally substituted with an arbitrary substituent, or silyl having 3 to 18 carbon atoms. R _{2 to} R ₅ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 8 carbon atoms,
Y and Z each independently represent a hydrogen atom, —COOR ₇ , or —CON (R ₈ ) ₂ , and at least one of Y and Z represents —COOR ₇ ;
Here, R ₇ is an alkyl group having 1 to 12 carbon atoms which may be substituted with an arbitrary substituent, —CH ₂ —CO—R ₉ (R ₉ is a straight chain or branched chain having 1 to 8 carbon atoms) Chain alkyl group), or the following formula:

In the above formula, R ₁₀ represents an alkylene group having 1 to 3 carbon atoms, R ₁₁ represents an alkyl group having 1 to 8 carbon atoms, and m is an integer of 1 to 4. R ₈ is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with any substituent, or the following formula:

In the above formula, R ₁₂ represents an alkylene group having 1 to 3 carbon atoms, R ₁₃ represents an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4. 2 R ₈ are not simultaneously hydrogen atoms,
In the formula (2), R _{1 ′} is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with any substituent, —CH ₂ —CO—R _{6 ′} (R _{6 ′} is a carbon atom) A linear or branched alkyl group having 1 to 8 carbon atoms), an acyl group having 1 to 10 carbon atoms, an allyl group, an optionally substituted phenyl group, or 3 to 3 carbon atoms. 18 represents a silyl group, R _{2 ′ to} R _{5 ′} each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 8 carbon atoms,
Y ′ and Z ′ each independently represent —COOR ₁₄ , —CH ₂ —CO—R ₁₅ , or —CON (R ₁₆ ) ₂ ;
Here, R ₁₄ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted with any substituent, or the following formula:

In the above formula, R ₁₇ represents an alkylene group having 1 to 3 carbon atoms, R ₁₈ represents an alkyl group having 1 to 8 carbon atoms, and l is an integer of 1 to 4. R ₁₅ represents a linear or branched alkyl group having 1 to 8 carbon atoms, and R ₁₆ is independently a hydrogen atom or an optionally substituted carbon atom having 1 to 1 carbon atoms. 12 alkyl groups or the following formula:

In the above formula, R ₁₉ represents an alkylene group having 1 to 3 carbon atoms, R ₂₀ represents an alkyl group having 1 to 8 carbon atoms, and k is an integer of 1 to 4. 2 R ₁₆ do not simultaneously become a hydrogen atom,
When either one of Y ′ and Z ′ is —COOH, the other is —CON (R ₁₆ ) ₂ , and X represents an arbitrary divalent linking group; The compound represented by the formula (1) is represented by the following formula (3) or (4):

In formula (3) or (4), R _{1 to} R ₅ , Y and Z are as defined in formula (1):
A compound represented by
The compound represented by the formula (2) is represented by the following formula (5) or (6):

In the formula (5) or (6), R _{1 ′ to} R _{5 ′} , Y ′ and Z ′ have the same meaning as in the formula (2):
The quinophthalone compound of Claim 1 which is a compound represented by these. The quinophthalone compound according to claim 1 or 2, wherein the total number of carbon atoms present in R ₁ , R ₇ and R ₈ ; or R _{1 '} , R ₁₄ , R ₁₅ and R ₁₆ is 8 or more.

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