JP2001207092A - Oil based ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oil based ink composition which has a good hue and can form images having high storage stability such as lightfastness. SOLUTION: This oil based ink composition comprises an oil based medium and a compound represented by the formula (wherein Ar is an aryl group or a heterocyclic group; X, Y, and Z are each a group forming a unsaturated hetero 5-membered ring together with two carbon atoms and may have a substituent; R is NHRa or CH(Rb)(Rc); one of Rb and Rc is a substituent having a Hammett's substituent constant σρ of 0.3-1.5 and the other of Rb and Rc is a hydrogen atom, an aryl group, a heterocyclic group or a substituent having a Hamett's substituent constant σρ of 0.3-1.5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oil-based ink composition, and more particularly, to an oil-based ink composition utilizing a hydrazone dye having a specific structure.

[0002]

2. Description of the Related Art An oil-based ink composition is generally a composition in which a colorant is dispersed or dissolved in an oil-based medium. Conventionally,
Various dyes are used as the coloring agent. However, when a conventional dye is used, there are problems such as that the hue of the oil-based ink composition is slightly unclear and light fastness is poor. In addition, since the dispersibility or dissolution stability of the dye in the oil medium is insufficient, when the oil ink composition is stored for a long period of time, the dye may be decolorized or discolored or separated from the oil medium. .

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an oil-based ink composition which can form an image having good hue and high storage stability such as light fastness.

[0004]

The above object can be attained by providing the following oil-based ink composition. (1) An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (1).

[0005]

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(In the general formula (1), Ar represents an aryl group
Or X represents a heterocyclic group, and X, Y and Z each represent two carbon atoms.
A group which forms an unsaturated 5-membered hetero ring with an atom
And X, Y and Z may have a substituent. R is-
NHR^aOr -CH (R^b) (R ^c). R^aIs the water
Element atom, aryl group, alkyl group, heterocyclic group, acyl
Group, carbamoyl group, alkoxycarbonyl group, aryl
Ruoxycarbonyl group, sulfamoyl group, alkyls
Ruphonyl group, arylsulfonyl group, -CN, alkyl
R represents a phosphoryl group or an aryl phosphoryl group;^bPassing
And R^cIs that the Hammett's substituent constant σp is 0.3.
3 to 1.5 substituents;^bAnd R^cThe other is hydrogen
Placement of atom, aryl group, heterocyclic group, or Hammet
Represents a substituent having a substitution constant σp of 0.3 to 1.5. (2) an oily medium and a compound represented by the following general formula (2)
And an oil-based ink composition.

[0007]

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(In the general formula (2), Ar and R have the same meanings as Ar and R in the general formula (1).
¹ and R ² are a hydrogen atom, an aryl group, an alkyl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group,
Acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group or -OH
Represents (3) An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (3).

[0009]

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(In the general formula (3), Ar, R and R
¹ has the same meaning as Ar, R and R ¹ in the general formula (2). (4) An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (4).

[0011]

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(In the general formula (4), Ar, R and R
¹ has the same meaning as Ar, R and R ¹ in the general formula (2), and R ³ represents a hydrogen atom, an aryl group, an alkyl group,
Represents a heterocyclic group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfonyl group, or an arylsulfonyl group. (5) An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (5).

[0013]

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[0014] (In the general formula (5), Ar, R, R 1 and R ² have the same meanings Ar, R, R ¹ and R ² in the general formula (2), R ³ is the formula ( R in 4)
Synonymous with ³ . (6) An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (6).

[0015]

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[0016] (In the general formula (6), Ar, R, Ar R 1 and R ² in the formula (2), R, the same meaning as that of R ¹ and R ^2.) (7) Ar is below The oil-based ink composition according to any one of the above (1) to (6), which is a group represented by the general formula (7).

[0017]

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(In the general formula (7), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ^{7 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom or a halogen atom. Atom, alkyl group, aryl group, acyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, An alkylphosphoryl group, an arylphosphoryl group, an amino group, —CN or —OH.) (8) Any one of the above (1) to (6), wherein Ar is a group represented by the following general formula (8). 3. The oil-based ink composition according to item 1.

[0019]

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(In the general formula (8), R ^{11 to} R ¹³ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group. Group, aryloxy group or -OH
And X represents an oxygen atom or a sulfur atom. (9) The oil-based ink composition according to any one of the above (1) to (6), wherein Ar is a group represented by the following general formula (9).

[0021]

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(In the general formula (9), R ¹⁵ represents a hydrogen atom or an alkyl group, and R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group. A group, an alkylthio group, an arylthio group or —OH, and Y represents an oxygen atom or a sulfur atom.) (10) An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (10) .

[0023]

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(In the above general formula (10), R ¹⁸ and R ¹⁹
Has the same meaning as R ⁵ and R ⁶ in the general formula (7), R ²⁰ and R ²¹ have the same meanings as R ⁷ to R ¹⁰ in the general formula (7), and R and R ¹ have the same meanings as in the general formula (7) It has the same meaning as R and R ¹ in 2). (11) An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (11).

[0025]

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(In the above general formula (11), R ¹⁸ and R ¹⁹
Has the same meaning as R ⁵ and R ⁶ in the general formula (7), R ²⁰ and R ²¹ have the same meanings as R ⁷ to R ¹⁰ in the general formula (7), and R and R ¹ have the same meanings as in the general formula (7) has the same meaning as R and R ¹ in 2), R ³ has the same meaning as R ³ in the general formula (4). )

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The oil-based ink composition of the present invention contains the compound represented by the general formula (1) as a dye. The compound represented by the general formula (1) has good hue and good light fastness. Therefore, when an image is formed using the oil-based ink composition of the present invention, the formed image has a good hue and the light stability of the image area is high. Further, since the compound has a good affinity for an oily medium, the oily ink composition of the present invention has good storage stability without separation of the oily medium and the pigment even when stored for a long period of time. . X, Y and Z in the 5-membered heterocyclic ring represented by the general formula (1) represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and at least one of X, Y and Z is a nitrogen atom, an oxygen atom And a heteroatom group consisting of a sulfur atom and X, Y and Z may be substituted with a substituent. When X, Y or Z is a carbon atom, examples of the substituent include the same substituents as R ¹ and R ^{2 in} the following general formula (2), and when X is a nitrogen atom, the substituent Examples include the same substituents as R ^{3 in} formula (4). Examples of the five-membered hetero ring include the following.

[0028]

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Among them, the following are preferred from the viewpoint of hue.

[0030]

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More specifically, the compounds represented by the general formula (1) include, for example, compounds represented by the general formulas (2) to (6). Among them, general formulas (3) and (4)
Are preferred in terms of hue and light fastness.

Next, the compounds represented by formulas (1) to (6), (10) and (11) will be described in detail. When Ra to Rc in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10), and (11) represent an aryl group, the aryl group includes an unsubstituted group. An aryl group and an aryl group having a substituent are included. When the aryl group has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group, a substituted amino group, and a substituted oxycarbonyl. Group, substituted oxysulfonyl group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, aryl group, hydroxy group, acyl group, acyloxy group, substituted sulfonyloxy group, substituted aminocarbonyloxy group, substituted phosphoryloxy group or- OH groups and the like.

Ra to Rc in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11)
The aryl group represented by is preferably an aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a 2-methylphenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, -Propoxyphenyl group, 2-isopropoxyphenyl group, 2-butoxyphenyl group, 2- (2-ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 2-undecyloxyphenyl group, 2-trifluoromethylphenyl Group, 2- (2-ethylhexyloxy) -5-chlorophenyl group, 2,2′-hexyloxy-3,5-dichlorophenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, -(Dibutylaminocarbonylethoxy) phenyl group, 2,4-dichlorophenyl group, 2,5-dic Lorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-nitrophenyl group, 3-cyanophenyl group, 3-trifluoromethylphenyl group, 3-methoxyphenyl group, 3-ethoxyphenyl group, 3-butoxyphenyl group, 3- (2 ′
-Ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3,4-
Dimethoxyphenyl group, 3,5-dibutoxyphenyl group,

3-octyloxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 3-
(Di-2-ethylhexylaminocarbonylmethoxy)
Phenyl, 3-dodecyloxyphenyl, 4-chlorophenyl, 4-cyanophenyl, 4-nitrophenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-iso Propoxyphenyl group, 4-butoxyphenyl group, 4-
(2-ethylhexyloxy) phenyl group, 4-isopentyloxyphenyl group, 4- (octadecyloxy)
Phenyl group, 4-benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylsulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4-
A (2-ethylhexyloxycarbonyl) phenyl group,
4-t-octylphenyl group, 4-fluorophenyl group, 3-acetylphenyl group, 2-acetylaminophenyl group, 2,4-di-t-pentylphenyl group, 4-
(2-ethylhexyloxy) carbonylphenyl group,
4-methylthiophenyl, 4- (4-chlorophenylthio) phenyl, hydroxyphenyl, phenylsulfonylphenyl, phenylsulfonyloxyphenyl, phenylcarbonyloxyphenyl, dimethylaminocarbonyloxyphenyl, butylcarbonyl An oxyphenyl group, and the like.

Ra to Rc in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11)
Represents a heterocyclic group, the heterocyclic group includes an unsubstituted heterocyclic group and a heterocyclic group having a substituent.
When the heterocyclic group has a substituent, examples of the substituent include a halogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and an alkoxy group. Group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkylphosphoryl group, arylphosphoryl group, amino group, -CN and the like. Examples of the hetero ring constituting the hetero ring group include a 5-membered ring and a 6-membered hetero ring containing nitrogen, sulfur, oxygen, or the like as a ring-constituting atom. For example, pyridine, thiophene, thiazole, furan, imidazole and the like,
These heterocycles may be fused with another heterocycle or carbocycle. Specific examples of the heterocyclic group include the following heterocyclic groups.

[0036]

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When Ra in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) represent an alkyl group, the alkyl group is unsubstituted. And an alkyl group having a substituent. When the alkyl group has a substituent, examples of the substituent include an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, and a halogen atom. The substituent further includes an alkyl group, an alkoxy group, a nitro group, a cyano group,
It may be substituted with a hydroxy group, a halogen atom or the like.

The alkyl group represented by Ra in the general formula (1) and R ^{1 to} R ³ in the general formulas (2) to (6), (10) and (11) may be linear or branched. But
It may have an unsaturated bond. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, a trifluoromethyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group Octadecyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, isopentyl group, heptyl group, nonyl group, undecyl group, Propenyl group, heptadecenyl group, t-octyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-
An ethylhexyloxycarbonylmethyl group, a 1- (ethoxycarbonyl) ethyl group, a 2 ′, 4′-diisopentylphenyloxymethyl group, a 2 ′, 4′-di-t-butylphenyloxymethyl group, an ethoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, butyldecyloxycarbonylethyl group, dibutylaminocarbonylmethyl group, dibenzylaminocarbonylethyl group, ethyloxycarbonylpropyl group, 2-ethylhexyloxycarbonylpropyl group, 2,4-di-t
-Amylphenyloxypropyl group, 1- (2 ′, 4 ′)
-Di-t-amylphenyloxy) propyl group, 2,4
-Di-t-butylphenyloxypropyl group, acetylaminoethyl group, N, N-dihexylaminocarbonylethyl group, 2,4-di-t-amyloxyethyloxycarbonylpropyl group, isostearyloxycarbonylpropyl group, 1 -(2,4-di-t-pentylphenyloxy) propyl group, 2,4-di-t-pentylphenyloxyethyloxycarbonylpropyl group, naphthyloxyethyloxycarbonylethyl group, N-methyl-N-phenylethyl Examples thereof include an oxycarbonylethyl group and a methanesulfonylaminopropyl group.

When Ra in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) represent an acyl group, the acyl group has no substituent. And an acyl group having a substituent. When the acyl group has a substituent, the substituent is preferably an alkoxy group, an aryloxy group, a halogen atom, an alkylthio group, an arylthio group, or an anilino group. As the acyl group, an acyl group having 2 to 20 carbon atoms is preferable. Examples include a noyl group, a 2-cyanopropanoyl group, and a 1,1-dimethylpropanoyl group. In addition, examples of the acyl group include the following acyl groups.

[0040]

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When Ra in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) represent a carbamoyl group, the carbamoyl group is not substituted. And a carbamoyl group having a substituent. When the carbamoyl group has a substituent,
As the substituent, an alkyl group and an aryl group are preferable. The carbamoyl group is preferably a carbamoyl group having a total of 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, an N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-2-ethylhexylcarbamoyl group, N-decylcarbamoyl group, N-
Octadecylcarbamoyl, N-phenylcarbamoyl, N-2-methylphenylcarbamoyl, N-2
-Chlorophenylcarbamoyl group, N-2-methoxyphenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyloxy) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3- Nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N-4-
Methoxycarbamoyl group, N-4- (2′-ethylhexyloxy) phenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N,
Examples thereof include an N-dibutylcarbamoyl group and an N, N-diphenylcarbamoyl group. The carbamoyl group also includes the following carbamoyl groups.

[0042]

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When Ra in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) represent an alkoxycarbonyl group, the alkoxycarbonyl group includes An unsubstituted alkoxycarbonyl group and an alkoxycarbonyl group having a substituent are included. When the alkoxycarbonyl group has a substituent, the substituent of the alkyl group (the alkyl group in the alkoxy portion) is preferably a halogen atom, an alkoxy group, or an aryloxy group. The alkoxycarbonyl group has a total carbon number of 2
~ 20 alkoxycarbonyl groups are preferred, for example,
Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenyloxyethyloxycarbonyl group, Examples include a phenyloxypropyloxycarbonyl group, a 2,4-di-t-amylphenyloxyethylcarbonyl group, a 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl group, an isostearyloxycarbonyl group, and the like.

When Ra in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) represent an aryloxycarbonyl group, Includes an unsubstituted aryloxycarbonyl group and a substituted aryloxycarbonyl group. When the aryloxycarbonyl group has a substituent, the substituent of the aryl group (the aryl group in the aryloxy moiety) is preferably a halogen atom, an alkyl group, an alkoxy group, or an acylamino group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having a total of 7 to 30 carbon atoms, such as a 2-methylphenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2,6-dimethylphenyloxycarbonyl group, , 4,6-trimethylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 2,2-ethylhexylphenyloxy Carbonyl, 3- (2-ethylhexyloxy) phenyloxycarbonyl, 4-fluorophenyloxycarbonyl, 4-chlorophenyloxycarbonyl, 4-cyanophenyloxycarbonyl,
-Butoxyphenyloxycarbonyl group and the like.

When Ra in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) represent a sulfamoyl group, the sulfamoyl group is not substituted. And a sulfamoyl group having a substituent. When the sulfamoyl group has a substituent, the substituent is preferably an alkyl group or an aryl group. The sulfamoyl group is preferably a sulfamoyl group having a total of 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an N, N-dialkylsulfamoyl group, , N-diarylsulfamoyl group, N-
And an alkyl-N-arylsulfamoyl group. More specifically, an N-methylsulfamoyl group, N
-Ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group,
N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N
-Octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2-methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2
-Methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-2- (2-ethylhexyloxy) phenylsulfamoyl group, N-
3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxysulfamoyl group,
N-4- (2'-ethylhexyloxy) phenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N,
N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group,
And N, N-di- (2-ethylhexyl) sulfamoyl group.

When Ra in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) represent an alkylsulfonyl group, the alkylsulfonyl group includes Unsubstituted alkylsulfonyl groups and substituted alkylsulfonyl groups are included. As the alkylsulfonyl group, an alkylsulfonyl group having a total carbon number of 1 to 20 is preferable. Examples include an octylsulfonyl group, a 2-ethylhexylsulfonyl group, a decanoylsulfonyl group, a dodecanoylsulfonyl group, an octadecanoylsulfonyl group, and a cyanomethylsulfonyl group.

When Ra in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) represent an arylsulfonyl group, the arylsulfonyl group includes: Unsubstituted arylsulfonyl groups and substituted arylsulfonyl groups are included. When the arylsulfonyl group has a substituent, the substituent is preferably a halogen atom, an alkoxy group, an aryloxy group, a cyano group, a trifluoromethyl group, or a nitro group. As the arylsulfonyl group, an arylsulfonyl group having a total of 6 to 30 carbon atoms is preferable. , 2-methoxyphenylsulfonyl, 2-butoxyphenylsulfonyl, 3-chlorophenylsulfonyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3- (2-ethylhexyloxy) phenylsulfonyl, 3 -Nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-butoxyphenylsulfonyl group, 4- (2-
Ethylhexyloxy) phenylsulfonyl group, 4-octadecylphenylsulfonyl group and the like.

When ^Ra in the general formula (1) represents an alkyl phosphoryl group, the alkyl phosphoryl group includes an unsubstituted alkyl phosphoryl group and an alkyl phosphoryl group having a substituent. The alkyl phosphoryl group is preferably an alkyl phosphoryl group having a total of 2 to 40 carbon atoms, for example, a methyl phosphoryl group, an ethyl phosphoryl group, a propyl phosphoryl group, an isopropyl phosphoryl group, a butyl phosphoryl group, an isobutyl phosphoryl group,
sec-butyl phosphoryl group, t-butyl phosphoryl group, pentyl phosphoryl group, isopentyl phosphoryl group, hexyl phosphoryl group, heptyl phosphoryl group, octyl phosphoryl group, 2-ethylhexyl phosphoryl group, decyl phosphoryl group, dodecyl phosphoryl group, octadecyl phosphoryl group An ethoxycarbonylmethyl phosphoryl group, a 2-ethylhexyloxycarbonylmethyl phosphoryl group, an aminocarbonylmethyl phosphoryl group,
N, N-dibutylaminocarbonylmethylphosphoryl group, N-methylaminocarbonylmethylphosphoryl group,
N-ethylaminocarbonylmethylphosphoryl group, N-
Examples include an octylaminocarbonylmethylphosphoryl group and a benzylphosphoryl group.

When R ^a in the general formula (1) represents an arylphosphoryl group, the arylphosphoryl group includes an unsubstituted arylphosphoryl group and an arylphosphoryl group having a substituent. As the arylphosphoryl group, an arylphosphoryl group having a total carbon number of 12 to 50 is preferable. For example, a phenylphosphoryl group, a 1-naphthylphosphoryl group, a 2-naphthylphosphoryl group, a 2-chlorophenylphosphoryl group, a 2-methylphenylphosphoryl group , 2-methoxyphenyl phosphoryl, 2-butoxyphenyl phosphoryl, 3-chlorophenyl phosphoryl, 3-trifluoromethylphenyl phosphoryl, 3-cyanophenyl phosphoryl, 3- (2-ethylhexyloxy) phenyl phosphoryl, 3 -Nitrophenylphosphoryl group, 4-fluorophenylphosphoryl group, 4-cyanophenylphosphoryl group, 4-butoxyphenylphosphoryl group, 4- (2-ethylhexyloxy) phenylphosphoryl group, 4-octadecylphenyl Niruhosuhoriru group, and the like.

The substituent having a Hammett's substituent constant σp of 0.3 to 1.5 represented by R ^b and R ^c in the general formula (1) includes a cyano group, a nitro group and a sulfonyl group (for example, octyl) Sulfonyl, phenylsulfonyl, trifluoromethylsulfonyl, pentafluorophenylsulfonyl, etc.), β-carboxyvinyl group, sulfinyl group (eg, t-butylsulfinyl, tolylsulfinyl, trifluoromethylsulfinyl, pentafluorophenylsulfinyl, etc.), β, β-dicyanovinyl group, alkyl halide group (eg, trifluoromethyl, perfluorooctyl, ω-hydroperfluorododecyl, etc.), formyl group, carboxyl group, carbonyl group (eg, acetyl, pivaloyl, benzoyl, trifluoroacetyl) etc), Alkyl or aryloxycarbonyl group (for example, ethoxycarbonyl, phenoxycarbonyl, etc.), 1-tetrazolyl group, 5-chloro-1
A tetrazolyl group, a carbamoyl group (eg, dodecylcarbamoyl, phenylcarbamoyl, etc.), a sulfamoyl group (eg, trifluoromethylsulfamoyl,
Phenylsulfamoyl, ethylsulfamoyl and the like). Among them, a cyano group, a sulfonyl group, a sulfinyl group, a trifluoromethyl group, an alkyl or aryloxycarbonyl group, a carbamoyl group and a sulfamoyl group are preferable, and a cyano group and a sulfonyl group are particularly preferable.

The general formulas (2) to (6), (10), (1)
When R ¹ and R ² in 1) represent an acyloxy group, the acyloxy group includes an unsubstituted acyloxy group and an acyloxy group having a substituent. When the acyloxy group has a substituent, as the substituent,
A halogen atom, an alkoxy group and an aryloxy group are preferred. As the acyloxy group represented by R ² , an acyloxy group having a total of 2 to 20 carbon atoms is preferable. For example, an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group Octanoyloxy group, decanoyloxy group, undecanoyloxy group, octadecanoyloxy group and the like.

The general formulas (2) to (6), (10) and (1)
When R ¹ and R ² in 1) represent an alkoxy group,
The alkoxy group includes an unsubstituted alkoxy group and an alkoxy group having a substituent. When the alkoxy group represents a substituent, the substituent is preferably a halogen atom, an alkoxy group, or an aryloxy group.
As the alkoxy group, an alkoxy group having a total of 1 to 30 carbon atoms is preferable, for example, a methoxy group, an ethoxy group,
Propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group,
2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyloxy group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group,
N, N-dibutylaminocarbonylmethyloxy group, N
-Methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group, N-methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group,
And a cyanomethyloxy group.

The general formulas (2) to (6), (10), and (1)
When R ¹ and R ² in 1) represent an aryloxy group, the aryloxy group includes an unsubstituted aryloxy group and an aryloxy group having a substituent. When the aryloxy group has a substituent, the substituent is preferably a halogen atom, an alkoxy group, a cyano group, a trifluoromethyl group, an aryloxy group, or a nitro group. The aryloxy group includes a total of 6 to 3 carbon atoms.
And an aryloxy group of 0 is preferable, for example, phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyl Oxy group, 3-chlorophenyloxy group, 3
-Trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3- (2-ethylhexyloxy) phenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4- Butoxyphenyloxy group, 4- (2-ethylhexyloxy) phenyloxy group, 4-octadecylphenyloxy group and the like.

The general formulas (2) to (6), (10) and (1)
When R ¹ and R ² in 1) represent an alkylthio group, the alkylthio group includes an unsubstituted alkylthio group and an alkylthio group having a substituent. When the alkylthio group has a substituent, the substituent includes:
A carbonyl group, an alkoxy group and an aryloxy group are preferred. The alkylthio group has a total carbon number of 1 to 30.
Are preferred, for example, a methylthio group,
Ethylthio, propylthio, isopropylthio,
Butylthio, isobutylthio, sec-butylthio, t-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, 2-ethylhexylthio, decylthio, dodecylthio, octadecylthio, Ethoxycarbonylmethylthio, 2-ethylhexyloxycarbonylmethylthio, aminocarbonylmethylthio, N, N-
Dibutylaminocarbonylmethyl group, N-methylaminocarbonylmethylthio group, N-ethylaminocarbonylmethylthio group, N-octylaminocarbonylmethylthio group, N-methyl-N-benzylaminocarbonylmethylthio group, benzylthio group, cyanomethylthio group, etc. No.

The general formulas (2) to (6), (10), (1)
When R ¹ and R ² in 1) represent an arylthio group, the arylthio group includes an unsubstituted arylthio group and an arylthio group having a substituent. When the arylthio group has a substituent, the substituent includes:
Preferred are a halogen atom, an alkyl group, an aryloxy group, an alkoxy group, a cyano group, a trifluoromethyl group and a nitro group. The arylthio group has a total carbon number of 6 to
30 arylthio groups are preferred, for example, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group,
Chlorophenylthio group, 2-methylphenylthio group, 2
-Methoxyphenylthio, 2-butoxyphenylthio, 3-chlorophenylthio, 3-trifluoromethylphenylthio, 3-cyanophenylthio, 3-
(2-ethylhexyloxy) phenylthio group, 3-nitrophenylthio group, 4-fluorophenylthio group,
-Cyanophenylthio group, 4-butoxyphenylthio group, 4- (2-ethylhexyloxy) phenylthio group, 4-octadecylphenylthio group and the like.

The general formulas (2) to (6), (10), (1)
When R ¹ and R ² in 1) represent an amino group, the amino group includes an unsubstituted amino group and an amino group having a substituent. When the amino group has a substituent,
As the substituent, an alkyl group and an aryl group are preferable. Examples of the amino group, the amino group having a total carbon number of 0-50 is preferable, for example, -NH _2, N- alkylamino group, N- arylamino group, N- acylamino group, N-
A sulfonylamino group, an N, N-dialkylamino group,
An N, N-diarylamino group, an N-alkyl-N-arylamino group, an N, N-disulfonylamino group and the like can be mentioned. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-tertbutylamino group, N-hexylamino group, N-cyclohexylamino group, -Octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenyl Amino group, N
-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyloxy) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N -3-cyanophenylamino group, N-4-methoxyamino group, N
-4- (2'-ethylhexyloxy) phenylamino group, N-4-cyanophenylamino group, N-methyl-N
-Phenylamino group, N, N-dimethylamino group, N,
N-dibutylamino group, N, N-diphenylamino group,
N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group,
N, N- (di-2-ethylhexylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N
-(Diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (2-ethylhexylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like. In addition, examples of the amino group include the following amino groups.

[0057]

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[0058]

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R and R ^{1 to} R ³ may be a divalent linking group, or may link two molecules of an azo dye structure.

In the general formulas (1) to (6), Ar represents an aryl group or a heterocyclic group. The aryl group represented by Ar includes an unsubstituted aryl group and an aryl group having a substituent. When Ar represents an alkyl group having a substituent, examples of the substituent include a halogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkoxy group, Aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylphosphoryl, arylphosphoryl, amino, -C
N, -OH and the like. Examples of the aryl group include a benzene ring, a naphthalene ring, and an anthracene ring.

When Ar represents an aryl group, preferred is 1
The following are mentioned as a valent aryl group.

[0062]

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[0063]

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Preferred examples of the divalent aryl group include the following.

[0065]

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The heterocyclic group represented by Ar includes an unsubstituted heterocyclic group and a substituted heterocyclic group. When Ar represents a heterocyclic group having a substituent, examples of the substituent include the same substituents as the examples of the substituent when Ar represents an aryl group having a substituent. Examples of the hetero ring constituting the hetero ring group include a 5-membered ring and a 6-membered hetero ring containing nitrogen, sulfur, oxygen or the like as a ring-constituting atom. For example, pyridine, thiophene, thiazole, furan, imidazole and the like can be mentioned, and these heterocycles may be condensed with another heterocycle or carbocycle.

When Ar represents a heterocyclic group, preferred is 1
The following are examples of the valent heterocyclic group.

[0068]

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In the general formulas (1) to (6),
Ar is preferably any of the general formulas (7) to (9).

In the general formula (7), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group. As for the alkyl group and the aryl group represented by R ⁵ and R ^6, Ra to Rc in the general formula (1) and R ¹ to R 6 in the general formulas (2) to (6), (10), and (11) are used.
Each has the same meaning as the alkyl group and the aryl group represented by R ³ , and specific examples thereof include the same as described above.

R ^{7 to} R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkoxy group, Aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkylphosphoryl group, arylphosphoryl group,
Represents an amino group, -CN or -OH. About these substituents, except for a halogen atom, an alkylphosphoryl group, an arylphosphoryl group, and -CN, general formulas (2) to
(6), (10), and (11) have the same meanings as the respective substituents represented by R ^{1 to} R ² , and specific examples thereof include the same ones as described above. When R ^{7 to} R ¹⁰ represent a halogen atom, the halogen atom includes a fluorine atom, a chlorine atom,
A bromine atom and the like are mentioned, and a fluorine atom and a chlorine atom are preferable. When R ^{7 to} R ¹⁰ represent an alkylphosphoryl group, the alkylphosphoryl group has the same meaning as the alkylphosphoryl group represented by ^Ra in the general formula (1), and specific examples thereof include the same as those described above. . Also, R ⁷
When -R ¹⁰ represents an arylphosphoryl group, the arylphosphoryl group has the same meaning as the arylphosphoryl group represented by ^Ra in the general formula (1), and specific examples thereof include the same ones as described above.

In the general formula (8), R ^{11 to} R ¹³ each independently represent a hydrogen atom, an alkyl group or an aryl group. As for the alkyl group and the aryl group represented by R ^{11 to} R ^13, Ra to Rc in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10) and (11) are used.
Has the same meaning as an alkyl group and an aryl group represented by
Specific examples include the same as described above.

In the general formula (8), R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Represents an aryloxy group or -OH. When R ¹⁴ represents a halogen atom, the halogen atom includes a fluorine atom,
Examples thereof include a chlorine atom and a bromine atom, and a fluorine atom and a chlorine atom are preferred. When R ¹⁴ represents an alkyl group or an aryl group, for the alkyl group and the aryl group,
The alkyl groups and the aryl groups represented by Ra to Rc in the general formula (1) and R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10), and (11) have the same definitions, and specific examples. And the same as those described above. When R ¹⁴ represents an alkoxy group, R ¹⁴ is represented by —OR ²⁴ . R ²⁴
Represents an alkyl group; Ra in the general formula (1);
And R in general formulas (2) to (6), (10), and (11)
It has the same meaning as the alkyl group represented by ^{1 to} R ³ , and specific examples include the same as those described above. When R ¹⁴ represents an aryloxy group, R ¹⁴ is represented by —OR ²⁵ . R ²⁵ represents an aryl group, and Ra to R in the aforementioned general formula (1)
c, and general formulas (2) to (6), (10), (11)
Has the same meaning as the aryl group represented by R ^{1 to} R ³ , and specific examples thereof include the same ones as described above.

In the general formula (8), X represents an oxygen atom or a sulfur atom.

In the general formula (9), R ¹⁵ represents a hydrogen atom or an alkyl group. The alkyl group represented by R ¹⁵ has the same meaning as Ra in the general formula (1) and the alkyl group represented by R ^{1 to} R ^{3 in the} general formulas (2) to (6), (10), and (11). Specific examples include those similar to the above.

In the general formula (9), R¹⁶And R¹⁷Is each
Each independently represents a hydrogen atom, a halogen atom, an alkyl group,
Reel group, alkoxy group, aryloxy group, alkyl
Represents a thio group, an arylthio group or -OH. R¹⁶And
And R¹⁷Represents a halogen atom, an alkyl group, an aryl group,
For the alkoxy group and the aryloxy group,
R of the general formula (8)¹⁴Is the same as each substituent represented by
Also, specific examples include the same as described above.
R¹⁶And R¹⁷Represents an alkylthio group, ¹⁶And
And R¹⁷Is -SR²⁶It is represented by R²⁶Is alkyl
Ra represents a group represented by the general formula (1), and
R in formulas (2) to (6), (10), and (11)¹~ R^ThreeIs a table
Synonymous with the alkyl group, and specific examples thereof are the same as those described above.
And the like. R¹⁶And R¹⁷Is arylthio
When representing a group, R¹⁶And R¹⁷Is -SR²⁸In table
Is done. R²⁸Is an aryl group, and in the general formula (1),
Ra to Rc in general formulas (2) to (6), (1)
0), R in (11)¹~ R^ThreeHas the same meaning as the aryl group represented by
Also, specific examples include the same as described above.

In the general formula (9), Y represents an oxygen atom or a sulfur atom.

Hereinafter, specific examples of the compound represented by the general formula (1) will be given, but the compounds used in the ink for ink-jet recording of the present invention are not limited to the following specific examples. Specific examples of the Ar portion of the compound represented by the general formula (1) are shown in Chemical formulas 34 to 54, and specific examples of the five-membered heterocyclic moiety are shown in Tables 1 to 26. As specific examples of the compound represented by the general formula (1), specific examples 1 to 438 of an Ar moiety and specific examples (1) to a hetero five-membered ring moiety are given.
All of the various combinations with (123) are included. For example, the specific example 3 of the Ar moiety and the specific example (1
0) and the exemplified compound 3- (10) or Ar
Specific example 36 of the moiety and specific example (86) of the five-membered heterocyclic moiety
Compound 36- (86) (Chem. 5)
5) and the like. In addition, the structures of the compounds are specified by using the same expressions for the exemplified compounds shown in Examples described later.

[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3]

[0103]

[Table 4]

[0104]

[Table 5]

[0105]

[Table 6]

[0106]

[Table 7]

[0107]

[Table 8]

[0108]

[Table 9]

[0109]

[Table 10]

[0110]

[Table 11]

[0111]

[Table 12]

[0112]

[Table 13]

[0113]

[Table 14]

[0114]

[Table 15]

[0115]

[Table 16]

[0116]

[Table 17]

[0117]

[Table 18]

[0118]

[Table 19]

[0119]

[Table 20]

[0120]

[Table 21]

[0121]

[Table 22]

[0122]

[Table 23]

[0123]

[Table 24]

[0124]

[Table 25]

[0125]

[Table 26]

[0126]

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In the oil-based ink composition of the present invention, the compound represented by the formula (1) is preferably contained in an amount of 1 to 20% by weight, more preferably 2 to 10% by weight. When the compound represented by the general formula (1) is used alone, yellow, red, magenta, and blue hues are obtained, but other dyes may be mixed for hue adjustment. .

The oil-based ink composition of the present invention is obtained by dissolving or dispersing the compound represented by the general formula (1) in an oil-based medium. The oily medium may be a solid or liquid at normal temperature.
Those which are solid at room temperature are preferably those which melt and undergo a phase change to liquid or amorphous by application of heat in the image recording step.

Examples of solid oily media include beeswax, carnauba wax, rice wax, wood wax, jojoba oil, spermaceti, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, and microcrystalline wax. , Petrolactam, etc .; organic acids such as polyethylene wax, chlorinated hydrocarbons, palmitic acid, stearyl acid, behenic acid, tiglic acid, 2-acetonaphthobehenic acid, 12-hydroxystearic acid, dihydroxystearic acid; dodecanol , Tetradecanol, hexadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicoseno , Docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesicerin, hexanediol, decanediol, tetradecanediol, hexadecanediol, docosandiol, tetracosandiol, televisionneol, phenylglycerin, eicosandi Alcohols such as all, octanediol and phenylpropylene glycol;

Phenols such as bisphenol A and p-α-cumylphenol; organic acid esters of the above organic acids such as glycerin, ethylene glycol and diethylene glycol; cholesterol stearate, cholesterol palmitate, cholesterol myristate, cholesterol behenate; Cholesterol fatty acid esters such as cholesterol laurate and cholesterol melicate; saccharose stearate, saccharose palmitate, saccharose behenate, saccharose laurate, saccharose melinate, lactose stearate, lactose palmitate, lactose behenate, lactose laurate, melisin Saccharide fatty acid esters such as acid lactose; benzoylacetone, diacetbenzene, benzophenone, Kosanon, heptacosanone,
Ketones such as heptatriacontanone, hentriacontanone, stearone, laurone; oleamide;
Lauric amide, stearic amide, ricinoleamide, palmitic amide, tetrahydrofuran amide, erucamide, myristic amide, 12-hydroxystearic amide, N-stearyl erucamide, N-oleyl stearamide, N , N-ethylenebislauric acid amide, N, N-ethylenebisstearic acid amide, N, N-ethylenebisbehenic acid amide, N, N-xylylenebisstearic acid amide,
N-butylenebisstearic acid amide, N, N-dioleyladipamide, N, N-dioleylsebacic amide, N, N-distearylsebacic amide,
N-distearyl terephthalamide, phenacetin,
Amides such as toluamide and acetamide; sulfonamides such as p-toluenesulfonamide, ethylbenzenesulfonamide and butylbenzenesulfonamide;
α-methylnaphthalene, β-methylnaphthalene, 2,6
-Alkyl naphthalenes such as dimethyl naphthalene; carboxylic esters such as dibutyl naphthalate, dioctyl phthalate, dibutyl adipate, dimethyl terephthalate, benzyl benzoate, and methyl naphthalene-2,6-dicarboxylate; tributyl phosphate;
Phosphate esters such as triphenyl phosphate;

Examples of the liquid oily medium include a mixed solvent of one or more organic solvents. Examples of the organic solvent include alcohols such as ethanol, pentanol, heptanol, octanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol and anis alcohol; ethylene glycol monoethyl ether, ethylene glycol monophenyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol Monoethyl ether ace Over DOO, glycol derivatives such as propylene glycol diacetate;

Ketones such as benzyl methyl ketone, diacetone alcohol and cyclohexanone; ethers such as butyl phenyl ether, benzyl ethyl ether and hexyl ether; ethyl acetate, amyl acetate, benzyl acetate, phenyl ethyl acetate, phenyl ethyl acetate, phenoxyethyl acetate;
Ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate, isopropyl myristate, isopropyl palmitate, triethyl phosphate, tributyl phosphate, tricresyl phosphate, diethyl phthalate, phthalic acid Dibutyl, diethyl malonate, dipropyl malonate, diethyl diethylmalonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate,
Diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate,
Esters such as dioctyl fumarate and 3-hexenyl cinnamate; hydrocarbon solvents such as petroleum ether, petroleum benzyl, tetralin, delican, 1-amylbenzene, dimethylnaphthalene; acetonitrile, formamide;
N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, N-
Polar solvents such as vinyl-2-pyrrolidone and N, N-diethyldodecaneamide; These solvents may be used alone or as a mixture of two or more.

As the oily medium, it is preferable to use a medium having a relatively low melting point (softening point) (for example, 70 ° C. or lower) and a medium having a relatively high melting point (softening point) (120 to 200 ° C.).
When used together, the robustness of the image portion of the formed image is improved, and color transfer or the like is unlikely to occur even when a plurality of recording papers on which the images are formed are superposed. The oil medium preferably contains a polyamide, polyurethane, polyester, epoxy or polyacryl resin compatible with the oil medium used. By using the resin in combination, the film strength of the oil-based ink can be further increased. The resin is preferably contained in an amount of 0.5 to 20% by weight based on the total weight of the oil-based ink composition of the present invention. Further, an additive having an effect of improving the fastness of the dye, an antioxidant, a singlet oxygen quencher, an ultraviolet absorber and the like may be coexisted.

The oil-based ink composition of the present invention can be prepared by dissolving or dispersing the compound represented by the general formula (1) in a liquid or solid oil-based medium. When the oily medium is a solid, it is preferable that the compound represented by the general formula (1) is dissolved in the liquid medium after heating and melting the liquid medium. The oil-based medium of the oil-based ink composition of the present invention is described in JP-A-9-176532.
The vehicle described in the official gazette can be used.
The method described in the above publication can be used for the method for producing the oil-based ink composition of the present invention.

The oil-based ink composition of the present invention can be used as an ink for inkjet recording. In particular,
When the oily medium is solid at normal temperature, it can be used as an ink composition for a so-called hot melt type (or wax jet type) ink jet recording apparatus. Further, the oil-based ink composition of the present invention can be used as an ink sheet for melt-type thermal transfer by coating or impregnating a base material such as a cloth or a plastic film.
Further, it can be used as a ballpoint pen ink and a marker ink.

[0136]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. <Example 1> 1-methylnaphthalene 35 parts by weight 2,6-dimethylnaphthalene 60 parts by weight Dye (exemplified compound 62- (82)) 5 parts by weight A mixture of the above composition was stirred at 60 ° C for 5 hours and 1-methyl The dye was dissolved in an oil medium of naphthalene and 2,6-dimethylnaphthalene to obtain an oil ink composition. this,
Hot melt inkjet printer “JOLT”
SJ01A PS2 "(trade name, product of Hitachi Koki Co., Ltd.)
Was used to print on electrophotographic paper (product of Xerox Corporation). When the image portion of the formed image was visually observed, there was no blur in the image portion, and the image had a good magenta hue. After the image was recorded, the image portion was rubbed with the hand 10 seconds later. As a result, no stain was generated on the background portion around the image and the rubbed hand. Furthermore, irradiation was performed for 100 hours using a xenon fade meter (product of Suga Test Instruments Co., Ltd.).
The discoloration of the image was small. In addition, the above ink composition
After storage at 0 ° C. for 3 months, no separation of the dye and the medium occurred.

<Example 2> Dibutyl naphthalate 50 parts by weight Naphthalene-2,6-dicarboxylic acid diethyl ester 43 parts by weight Dye (exemplified compound 62- (82)) 7 parts by weight Example using a mixture of the above composition In the same manner as in Example 1, an oil-based ink composition was prepared. When the same evaluation was performed on the obtained oil-based ink composition, good results were obtained as in Example 1.

<Example 3> Dibutyl adipate 30 parts by weight Benzyl benzoate 63 parts by weight Dye (exemplified compound 62- (82)) 7 parts by weight An oil-based ink composition was prepared in the same manner as in Example 1 using the mixture having the above composition. Was prepared. When the same evaluation was performed on the obtained oil-based ink composition, good results were obtained as in Example 1.

<Example 4> Benzyl benzoate 40 parts by weight 2-methylnaphthalene 20 parts by weight Stearamide 35 parts by weight Dye (exemplified compound 62- (82)) 5 parts by weight Example 1 was prepared using a mixture having the above composition. In the same manner as in the above, an oil-based ink composition was prepared. When the same evaluation was performed on the obtained oil-based ink composition, good results were obtained as in Example 1.

Example 5 Tricresyl phosphate 65 parts by weight Dibutyl adipate 31 parts by weight Dye (exemplified compound 62- (82)) 4 parts by weight An oil-based ink composition was prepared in the same manner as in Example 1 using the mixture having the above composition. A product was made. When the same evaluation was performed on the obtained oil-based ink composition, good results were obtained as in Example 1.

<Examples 6 to 20> As shown in Table 27 below, the oil-based ink compositions of Examples 6 to 20 were prepared according to any of the formulations of Examples 1 to 5, except that only the dye was changed. did. When an image was formed using the obtained oil-based ink composition in the same manner as in Example 1, the hue of the obtained image portion was a good cyan hue.

[0142]

[Table 27]

<Examples 21 to 30> Oil-based ink compositions of Examples 21 to 30 were prepared in the same manner as in Example 1 except that the dyes were changed as shown in Table 28 below. When an image was formed using the obtained oil-based ink composition in the same manner as in Example 1, the obtained image portions had good hues.

[0144]

[Table 28]

Example 31 1-methylnaphthylene 35 parts by weight 2,6-dimethylnaphthalene 55 parts by weight Dye A (exemplified compound 62- (82)) 3 parts by weight Dye B (compound represented by the following structural formula) 3 parts by weight Dye C (compound represented by the following structural formula) 4 parts by weight An oil-based ink composition (hue: black) was prepared in the same manner as in Example 1 using the mixture having the above composition. When the same evaluation was performed on the obtained oil-based ink composition, a good result was obtained in the same manner as in Example 1 (however, the hue of the image portion was black).

[0146]

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<Example 32> Dye A used in Example 31
(Exemplified compound 62- (82)) is replaced with Exemplified compound 60-
An oil-based ink composition (hue: black) was prepared in the same manner as in Example 31, except that (50) was used. When the same evaluation was performed on the obtained oil-based ink composition, a good result was obtained in the same manner as in Example 1 (however, the hue of the image portion was black).

<Example 33> Dye B used in Example 31
Was replaced with Exemplified Compound 62- (82).
An oil-based ink composition (hue: black) in the same manner as in Example 31 except that the dye 1 was changed to Exemplified Compound 63- (71).
Was prepared. When the same evaluation was performed on the obtained oil-based ink composition, a good result was obtained in the same manner as in Example 1 (however, the hue of the image portion was black).

Example 34 Tricresyl phosphate 60 parts by weight Dibutyl adipate 20 parts by weight Compound represented by the following structural formula 1 10 parts by weight Dye (exemplified compound 62- (82)) 5 parts by weight A mixture having the above composition was used. In the same manner as in Example 1, an oil-based ink composition (hue: cyan) was produced. When the same evaluation was performed on the obtained oil-based ink composition, good results were obtained as in Example 1.

[0150]

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<Example 35> Tricresyl phosphate 60 parts by weight 15 parts by weight of dibutyl adipate 10 parts by weight of the compound represented by the structural formula 1 10 parts by weight of the compound represented by the following structural formula 2 Dye (Exemplified compound 62- ( 82)) 5 parts by weight An oil-based ink composition (hue: cyan) was prepared in the same manner as in Example 1 using the mixture having the above composition. When the same evaluation was performed on the obtained oil-based ink composition, good results were obtained as in Example 1.

[0152]

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<Example 36> An oil-based ink was prepared in the same manner as in Example 35 except that the compound represented by Structural Formula 1 was used instead of the compound represented by Structural Formula 1. A composition (hue: cyan) was prepared. When the same evaluation was performed on the obtained oil-based ink composition, good results were obtained as in Example 1.

[0154]

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[0155]

According to the present invention, it is possible to provide an oil-based ink composition which can form an image having good hue and high storage stability such as light fastness.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Tetsunori Matsushita 200 Fujinaka Film Co., Ltd., Fujinomiya City, Shizuoka Prefecture (72) Inventor Akinori Fujita 200 Onakazato Fujinaka City, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H086 BA54 BA56 2H111 AA01 AA09 AA26 BA38 BA44 BA75 4J039 AB12 BC07 BC19 BC20 BC29 BC31 BC32 BC33 BC36 BC39 BC49 BC50 BC51 BC53 BC54 BC55 BC56 BC72 BC73 BC74 BC76 BC77 BC79 BE12 CA05 EA36 EA24 EA44 GA

Claims (11)

[Claims] 1. An oily medium represented by the following general formula (1)
An oil-based ink composition comprising: Embedded image(In the general formula (1), Ar represents an aryl group or a hetero group.
X, Y and Z represent two ring atoms
A group forming an unsaturated hetero 5-membered ring, X, Y and
And Z may have a substituent. R is -NHR^aOr
-CH (R^b) (R ^c). R^aIs a hydrogen atom, an ant
Group, alkyl group, heterocyclic group, acyl group, carbamo
Yl group, alkoxycarbonyl group, aryloxycal
Bonyl group, sulfamoyl group, alkylsulfonyl group,
Arylsulfonyl group, -CN, alkylphosphoryl
R represents an arylphosphoryl group;^bAnd R^cOne of
Is a Hammett's substituent constant σp of 0.3 to 1.5.
R represents a substituent^bAnd R^cThe other is a hydrogen atom,
Group, heterocyclic group, or Hammett's substituent constant σp
Represents a substituent of 0.3 to 1.5. ) 2. An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (2). Embedded image (In the general formula (2), Ar and R have the same meanings as Ar and R in the general formula (1), and R ¹ and R ² represent a hydrogen atom, an aryl group, an alkyl group, a heterocyclic group, an acyl group A carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group,
Represents an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group or -OH. ) 3. An oil-based ink composition comprising an oil-based medium and a compound represented by the following general formula (3). Embedded image (In the general formula (3), Ar, R and R ¹ are as defined Ar, and R and R ¹ in the general formula (2).) 4. An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (4). Embedded image (In the general formula (4), Ar, R and R ¹ have the same meanings Ar, and R and R ¹ in the general formula (2), R ³
Is a hydrogen atom, an aryl group, an alkyl group, a heterocyclic group,
Acyl group, carbamoyl group, alkoxycarbonyl group,
Represents an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfonyl group, or an arylsulfonyl group. ) 5. An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (5). Embedded image In (Formula (5), Ar, R, R ¹ and R ² have the same meanings Ar, R, R ¹ and R ² in the general formula (2), in R ³ is the formula (4) Synonymous with R ^3. ) 6. An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (6). Embedded image (In the general formula (6), Ar, R, R 1 and R ² are as defined Ar, R, R ¹ and R ² in the general formula (2).) 7. The oil-based ink composition according to claim 1, wherein Ar is a group represented by the following general formula (7). Embedded image (In the general formula ^{(7), R 5, R} 6 each independently represent a hydrogen atom, an alkyl group or an aryl group,, R ⁷ to R
¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, Represents an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylphosphoryl group, an arylphosphoryl group, an amino group, -CN or -OH. ) 8. The oil-based ink composition according to claim 1, wherein Ar is a group represented by the following general formula (8). Embedded image (In the general formula (8), R ^{11 to} R ¹³ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryl group. Represents an oxy group or -OH, and X represents an oxygen atom or a sulfur atom.) 9. The oil-based ink composition according to claim 1, wherein Ar is a group represented by the following general formula (9). Embedded image (In the general formula (9), R ¹⁵ represents a hydrogen atom or an alkyl group, and R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group. Group, an arylthio group or -OH, and Y represents an oxygen atom or a sulfur atom.) 10. An oil-based ink composition containing an oil-based medium and a compound represented by the following general formula (10). Embedded image (In the general formula (10), R ¹⁸ and R ¹⁹ have the same meanings as R ⁵ and R ⁶ in the general formula (7), and R ²⁰ and R ²¹ represent R ⁷ to R ¹⁰ in the general formula (7). in the above formula, R and R ¹ are the same as R and R ¹ in the general formula (2).) 11. An oil-based ink composition comprising an oil-based medium and a compound represented by the following general formula (11). Embedded image (In the general formula (11), R ¹⁸ and R ¹⁹ have the same meanings as R ⁵ and R ⁶ in the general formula (7), and R ²⁰ and R ²¹ represent R ⁷ to R ¹⁰ in the general formula (7). in the above formula, R and R ¹ have the same meanings as R and R ¹ in the general formula (2), R ³ has the same meaning as R ³ in the general formula (4).)