JP5727321B2 - Pyridone azo compounds - Google Patents

Description

  The present invention relates to a pyridone azo compound. More specifically, the present invention relates to a pyridone azo compound having excellent heat resistance.

  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. .

  For example, pyridone azo compounds are known as yellow dyes (see, for example, Patent Documents 1 to 3).

JP-A 61-159594 JP 2006-71822 A JP 2009-299030 A

  When dyes are used in inkjet ink applications, the performance required of the dyes has been mainly soluble in solvents, but in recent years, when printing materials are processed at high temperatures after inkjet printing (for example, in food containers) There is a growing need for heat resistance that is difficult to discolor even when the food container is heat sterilized after inkjet printing.

  However, the conventional pyridone azo compounds described in Patent Documents 1 to 3 have a drawback that they are poor in heat resistance as compared with phthalocyanine dyes and azo metal complex dyes. Therefore, development of pyridone azo compounds with improved heat resistance has been desired.

  Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a yellow dye having excellent heat resistance.

  The above purpose is expressed by the following formula (3 ′):

In the above formula (3 ′), R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms; R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. M is an integer from 1 to 3 and is achieved by a pyridone azo compound containing an alkoxysilyl group.

  According to the present invention, a yellow pigment excellent in heat resistance can be provided.

  The present invention relates to the following formula (3 '):

In the above formula (3 ′), R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms; R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. M is an integer of 1 to 3, and is a pyridone azo compound containing an alkoxysilyl group.

  As described above, the conventional pyridone azo compound has a drawback that it has poor heat resistance as compared with phthalocyanine dyes and azo metal complex dyes. Specifically, when heated, the pyridone azo compound tends to sublime or decompose, and as a result, discoloration or decoloration of the pigment occurs. Here, sublimation includes not only vaporization directly from a solid but also vaporization via liquefaction. In contrast, the pyridone azo compound of the present invention and the polymer obtained by subjecting the pyridone azo compound of the present invention to water treatment or acid treatment are excellent in heat resistance, sublimation resistance, and decomposition resistance. The mechanism is assumed to be as follows. However, such a mechanism is only speculation, and the technical scope of the present invention is not limited by such a mechanism.

  That is, the pyridone azo compound of the present invention has an alkoxysilyl group. When a pyridone azo compound into which an alkoxysilyl group has been introduced is heated, a small amount of moisture in the air acts as a catalyst, hydrolyzing the alkoxysilyl group, and subsequently forming a siloxane bond into a network by a dehydration condensation reaction. Forming a strong structure. Therefore, thermal decomposition can be suppressed, and since it becomes a polymer, sublimation due to high temperature is suppressed. Therefore, even when it is assumed that the substrate is subjected to high-temperature treatment after inkjet printing, such a pyridone azo compound can be suitably used in such applications as ink.

  In addition, when the pyridone azo compound of the present invention is placed in the presence of water or an acid (for example, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid; an organic acid such as lactic acid, citric acid or acetic acid) (in some cases When heated further), the alkoxysilyl group promotes hydrolysis and condensation reactions and forms a stronger structure than simply being heated. Therefore, thermal decomposition and sublimation can be suppressed rather than simply heating, and solvent resistance is improved.

  In addition, the pyridone azo compound of the present invention that has been treated with water, acid, or heat has reduced solubility in organic solvents such as cyclohexanone, acetone, and propylene glycol 1-monomethyl ether 2-acetate. In other words, when it is prepared as an ink-jet ink, it is before polymerization (in the monomer state), so solubility in the ink is ensured, but after printing, it is sprayed with water or treated with acid. Or by heating, the polymerization is accelerated and the solvent resistance is increased.

  Hereinafter, preferred embodiments of the present invention will be described.

  As described above, the present invention provides the following formula (3 '):

In the above formula (3 ′), R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms; R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. M is an integer of 1 to 3, and is a pyridone azo compound containing an alkoxysilyl group.

(R ³ )
R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms. Preferably, R ³ is a linear or branched alkyl group having 1 to 3 carbon atoms.

Here, the linear or branched alkyl group having 1 to 4 carbon atoms is not particularly limited. Specific examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these, in consideration of heat resistance such as heat resistance and solubility in organic solvents, specifically, a methyl group, an ethyl group, a propyl group, and the like are preferable. When a plurality of R ³ are present (m is 2 or 3), each R ³ may be the same or different.

(R ⁴ )
R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. The linear or branched alkyl group having 1 to 4 carbon atoms is preferably a linear or branched alkyl group having 1 to 3 carbon atoms.

Here, as the linear or branched alkyl group having 1 to 4 carbon atoms, those exemplified for R ³ can be preferably used, and among these, considering the solubility in an organic solvent, R ⁴ is Specifically, a methyl group, an ethyl group, a propyl group, and the like are preferable. When a plurality of R ⁴ are present (m is 1), each R ⁴ may be the same or different.

(M)
m is an integer of 1-3. When m is 1, 2 and 3, the pyridone azo compound of the present invention specifically has the following structure.

  Of these, m is preferably 2 or 3, and particularly preferably m is 3. As described above, even when the pyridone azo compound into which the alkoxysilyl group is introduced is heated, polymerization occurs before the sublimation or decomposition of the pyridone azo compound occurs, and as a result, sublimation or decomposition can be suppressed. Therefore, even if it is assumed that the printed material is subjected to high-temperature processing after inkjet printing, it can be suitably used in such applications as ink. Here, as the number of m increases, the alkoxysilyl group network becomes stronger, so that heat resistance and decomposition resistance can be further improved.

Here, a preferable combination of R ³ , R ⁴ , and m is as follows: R ³ is a methyl group, an ethyl group, or a propyl group; R ⁴ is a methyl group, an ethyl group, or a propyl group; . More preferably, R ³ is a methyl group or an ethyl group; R ⁴ is a methyl group, an ethyl group, or a propyl group; By such a combination, the heat resistance of the pyridone azo compound can be particularly improved.

  The pyridone azo compound of the present invention more preferably has a structure represented by the following formula (1), formula (1 '), formula (2) or formula (2').

In the above formula (1), formula (1 ′), formula (2) and formula (2 ′),
X represents the following formula (3):

It is group represented by these.

(Y)
Y is independently —CO— or —SO ₂ —. By being such, it has the effect of improving the solubility to an organic solvent. Here, “independently” is because the pyridone azo compound represented by (1 ′) has two groups represented by Y (Y is present in X).

(R ¹ )
R ¹ represents a hydrogen atom, a linear or branched alkyl group or a phenyl group having 1 to 5 carbon atoms.

The linear or branched alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 2 to 4 carbon atoms. Here, the linear or branched alkyl group having 1 to 5 carbon atoms is not particularly limited. Specific examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. And neopentyl group. Among these, in consideration of heat resistance such as heat resistance and solubility in an organic solvent, R ¹ is preferably a hydrogen atom, a methyl group or a phenyl group, and more from the viewpoint of coloring power as a dye. Preferably it is a hydrogen atom.

(R ² )
R ² is each independently a linear or branched alkylene group having 1 to 6 carbon atoms, or the following (4):

In this case, each R ² ′ is independently a linear or branched alkylene group having 1 to 6 carbon atoms. The linear or branched alkylene group having 1 to 6 carbon atoms in R ² is preferably a linear or branched alkylene group having 2 to 4 carbon atoms.

  Here, examples of the linear or branched alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a 1,2-propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. It is done. Among these, specifically considering heat resistance such as heat resistance and solubility in an organic solvent, an ethylene group, a trimethylene group, a 1,2-propylene group, a tetramethylene group, and the like are preferable.

(R ² ')
R ² ′ each independently represents a linear or branched alkylene group having 1 to 6 carbon atoms. Preferred examples of the linear or branched alkylene group having 1 to 6 carbon atoms include those listed for R ² . Among these, in consideration of heat resistance such as heat resistance and solubility in an organic solvent, an ethylene group, a trimethylene group, a 1,2-propylene group, a tetramethylene group, and the like are preferable independently.

(R ³ , R ⁴ , m)
R ³ has the same definition as above, R ⁴ has the same definition as above, and m has the same definition as above.

  As described above, in X represented by the formula (3), as described above, even when the pyridone azo compound is heated, polymerization occurs before sublimation or decomposition of the pyridone azo compound, and as a result, Sublimation and decomposition can be suppressed. Therefore, even if it is assumed that the printed material is subjected to high-temperature processing after inkjet printing, it can be suitably used in such applications as ink.

Here, in X, a preferable combination of Y, R ¹ , R ² , R ³ , R ⁴ and m is such that Y is —CO— or —SO ₂ —; R ¹ is a hydrogen atom, a methyl group or phenyl R ² is an ethylene group, trimethylene group, 1,2-propylene group, or tetramethylene group, or represented by formula (4), wherein R ² ′ is an ethylene group, trimethylene group, 1 , 2-propylene group or tetramethylene group; R ³ , R ⁴ and m are combinations described above. By such a combination, the heat resistance of the pyridone azo compound can be significantly improved.

(R ⁵ )
R ⁵ is each independently a halogen atom, NO ₂ , a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 12 carbon atoms. . By introducing R ^5, there is an effect that the absorption waveform can be shifted and the color can be adjusted according to the purpose.

  Here, the halogen atom is not particularly limited and may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. However, considering heat resistance such as heat resistance and solubility in an organic solvent, chlorine atom is particularly preferable. It is preferable that

  Further, the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms is preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and more preferably , A straight-chain, branched-chain or cyclic alkyl group having 1 to 3 carbon atoms.

  Here, the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms is not particularly limited, but is methyl group, ethyl group, 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, cyclopentyl group, n-hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl Group, dodecyl group, 2-ethylhexyl group and the like. Of these, when considering particularly heat resistance such as heat resistance and solubility in an organic solvent, specifically, a methyl group, an ethyl group, a propyl group, and the like are more preferable.

  In addition, the linear or branched alkoxy group having 1 to 12 carbon atoms has a structure in which such a linear or branched alkyl group having 1 to 12 carbon atoms is bonded to an oxygen atom. Of these, a methoxy group, an ethoxy group, and the like are preferable in consideration of heat resistance such as heat resistance and solubility in an organic solvent.

(R)
Each R is independently hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched hydroxyalkyl group having 2 to 16 carbon atoms, or a straight chain having 2 to 16 carbon atoms. A chain or branched alkoxyalkyl group.

  The linear or branched alkyl group having 1 to 16 carbon atoms is more preferably a linear or branched alkyl group having 2 to 10 carbon atoms, and further preferably a linear or branched chain having 3 to 6 carbon atoms. It is an alkyl group. Examples of the linear or branched alkyl group having 1 to 16 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group and the like. Among these, considering heat resistance such as heat resistance and solubility in organic solvents, specifically, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group N-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like are more preferable.

  The linear or branched hydroxyalkyl group having 1 to 16 carbon atoms is preferably a linear or branched hydroxyalkyl group having 2 to 5 carbon atoms. Although it does not restrict | limit especially as a C1-C16 linear or branched hydroxyalkyl group, For example, a hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-hydroxy Isopropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 4-hydroxy-3-methyl-butyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, 9-hydroxynonyl group, Examples include 10-hydroxydecyl group, 11-hydroxyundecyl group, 12-hydroxydodecyl group and the like. Among these, in consideration of heat resistance such as heat resistance and solubility in an organic solvent, specifically, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, and the like are preferable.

  The linear or branched alkoxyalkyl group having 2 to 16 carbon atoms is preferably a linear or branched alkoxyalkyl group having 3 to 14 carbon atoms, and a linear or branched alkoxyalkyl group having 4 to 10 carbon atoms. More preferably, it is an alkoxyalkyl group. The linear or branched alkoxyalkyl group having 2 to 16 carbon atoms is not particularly limited, and examples thereof include a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, a propoxybutyl group, and a propoxy group. A propyl group, i-propoxypropyl group, i-propoxypentyl group, t-butoxyethyl group, hexyloxybutyl group, 2-ethylhexyloxypropyl group and the like can be mentioned. Among these, considering heat resistance such as heat resistance and solubility in organic solvents, specifically, ethoxyethyl group, methoxypropyl group, i-propoxypropyl group, propoxypropyl group, 2-ethylhexyloxypropyl Groups and the like are preferred.

(P)
p is each independently an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. As described above, when one or more groups represented by the formula (3) having an alkoxysilyl group are introduced, the pyridone azo compound becomes a polymerizable pyridone azo compound. It becomes. In addition, when p is 2 or more, “Y, R ¹ , R ² , R ³ , R ⁴ , m” defined by X must be understood to be independent from each other. Y and R must also be understood to be independent of each other.

(Q)
q is each independently an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. R ⁵ is not an essential substituent, but when at least one of these substituents is introduced, there is an effect that the absorption waveform can be shifted and the color can be adjusted according to the purpose.

(R ⁶ )
Each R ⁶ is independently a linear or branched alkyl group having 1 to 8 carbon atoms.

  The linear or branched alkyl group having 1 to 8 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 3 carbon atoms. It is an alkyl group.

Here, the linear or branched alkyl group having 1 to 8 carbon atoms is not particularly limited. Specific examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. , Neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like. Among these, considering heat resistance such as heat resistance and solubility in an organic solvent, R ⁶ is more preferably a methyl group, an ethyl group, a propyl group, or the like.

(R ⁷ )
R ⁷ each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched aralkyl group having 7 to 16 carbon atoms, or a linear or branched chain having 2 to 16 carbon atoms. A hydroxyalkyl group having 2 to 16 carbon atoms, a linear or branched hydroxyalkoxyalkyl group having 2 to 16 carbon atoms, a linear or branched alkoxyalkyl group having 2 to 16 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, or —R ⁷ ′ —X, wherein R ⁷ ′ is a linear or branched alkylene group having 1 to 8 carbon atoms, and X has the same definition as above. In R 7 ^', preferably, a methylene group or an ethylene group, preferably an ethylene group.

  The linear or branched alkyl group having 1 to 16 carbon atoms is more preferably a linear or branched alkyl group having 2 to 12 carbon atoms, and further preferably a linear or branched chain having 2 to 10 carbon atoms. It is an alkyl group. Examples of the linear or branched alkyl group having 1 to 16 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group Group and the like. Among these, considering heat resistance such as heat resistance and solubility in organic solvents, specifically, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n -Pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like are more preferable.

  The linear or branched aralkyl group having 7 to 16 carbon atoms is preferably a linear or branched aralkyl group having 7 to 14 carbon atoms, more preferably a linear or branched chain having 7 to 12 carbon atoms. Specifically, phenylalkyl groups such as benzyl group, phenylpropyl group (1-methyl-3-phenylpropyl group, etc.), phenylbutyl group (3-amino-1-phenylbutyl group, etc.) Etc. are preferable.

  The linear or branched hydroxyalkyl group having 1 to 16 carbon atoms is preferably a linear or branched hydroxyalkyl group having 2 to 5 carbon atoms. Although it does not restrict | limit especially as a C1-C16 linear or branched hydroxyalkyl group, For example, a hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-hydroxy Isopropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 4-hydroxy-3-methyl-butyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, 9-hydroxynonyl group, Examples include 10-hydroxydecyl group, 11-hydroxyundecyl group, 12-hydroxydodecyl group and the like. Among these, in consideration of heat resistance such as heat resistance and solubility in an organic solvent, specifically, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, and the like are preferable.

  The linear or branched alkoxyalkyl group having 2 to 16 carbon atoms is preferably a linear or branched alkoxyalkyl group having 3 to 14 carbon atoms, and a linear or branched alkoxyalkyl group having 4 to 10 carbon atoms. More preferably, it is an alkoxyalkyl group. The linear or branched alkoxyalkyl group having 2 to 16 carbon atoms is not particularly limited, and examples thereof include a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, a propoxybutyl group, and a propoxy group. A propyl group, i-propoxypropyl group, i-propoxypentyl group, t-butoxyethyl group, hexyloxybutyl group, 2-ethylhexyloxypropyl group and the like can be mentioned. Among these, considering heat resistance such as heat resistance and solubility in organic solvents, specifically, ethoxyethyl group, methoxypropyl group, i-propoxypropyl group, propoxypropyl group, 2-ethylhexyloxypropyl Groups and the like are preferred.

  The linear or branched hydroxyalkoxyalkyl group having 2 to 16 carbon atoms is preferably a linear or branched hydroxyalkoxyalkyl group having 4 to 12 carbon atoms. Here, the “hydroxyalkoxyalkyl group” means an alkoxyalkyl group substituted with a hydroxy group. As the alkoxyalkyl group, those described above can be preferably used. Among these, in consideration of heat resistance such as heat resistance and solubility in an organic solvent, specifically, 2- (2-hydroxyethoxy) ethyl group and the like are preferable.

  The heterocyclic group having 2 to 10 carbon atoms includes, as the heterocyclic group, a heterocyclic group containing at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and a monocyclic heterocyclic group Not limited to, a condensed heterocyclic group in which a plurality of heterocyclic rings are condensed, or a heterocyclic ring and a hydrocarbon ring (non-aromatic hydrocarbon ring or aromatic hydrocarbon ring) are condensed (ortho condensation, ortho-and-peri condensation, etc.) It may be a condensed heterocyclic group. 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.

^(R 8)
R ⁸ is a linear or branched alkylene group having 1 to 12 carbon atoms, or the following formula (5):

In this case, each R ⁹ is independently a linear or branched alkylene group having 1 to 12 carbon atoms.

  The linear or branched alkylene group having 1 to 12 carbon atoms is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and a linear or branched alkylene group having 2 to 8 carbon atoms. It is more preferable that Examples of the linear or branched alkylene group having 1 to 12 carbon atoms include methylene group, ethylene group, trimethylene group, propane-1,2-diyl group, tetramethylene group, pentamethylene group, pentane-1,3-diyl. Group, hexamethylene group octamethylene group, and the like. Among these, in consideration of heat resistance such as heat resistance and solubility in organic solvents, specifically, an ethylene group, a tetramethylene group, a pentane-1,3-diyl group, a hexamethylene group, and the like are preferable.

(R ⁹ )
R ⁹ are each independently a linear or branched alkylene group having 1 to 12 carbon atoms, n is representative of the integer of 1 to 8. At this time, when it is ^{n ≧ 2 - (O-R} 9) n - in ^{R 9} it is also independent of each other. As the linear or branched alkylene group having 1 to 12 carbon atoms in R ⁹ , those described for R ⁸ are similarly applied. Of these, ethylene group, trimethylene group, tetramethylene group and the like are preferable in consideration of heat resistance such as heat resistance and solubility in organic solvents. n is an integer of 1 to 8, but in consideration of heat resistance such as heat resistance and solubility in an organic solvent, it is preferably an integer of 1 to 6, and an integer of 1 to 4. More preferred.

  Based on the above, specific examples of pyridone azo compounds preferred in the present invention are as follows.

  The pyridone azo compound as described above can achieve the intended object of the present invention.

  Hereinafter, preferred embodiments of the method for producing a pyridone azo compound of the present invention will be described. However, the present invention is not limited to the following preferred embodiments.

  For example, the following formula (6):

An amine compound 1 of the following formula (7):

The diazo compound of the amine compound 2 was obtained to obtain a diazo compound, and the obtained diazo compound was
Following formula (9):

A 3-cyano-6-hydroxypyridin-2 (1H) -one compound (also referred to herein simply as “(9) compound”), or the following formula (10):

And a pyridone azo compound of the present invention can be produced by coupling with the above compound (also referred to herein simply as “(10) compound”). Or following formula (8):

A diazo compound of the amine compound 3 is obtained to obtain a diazo compound.
Following formula (11):

Compound (also referred to herein simply as “(11) compound”), or
Following formula (12):

And a pyridone azo compound of the present invention can be produced by coupling with the above compound (also referred to herein simply as “(12) compound”). “Amine compound 1”, “amine compound 2”, and “amine compound 3” may be collectively referred to simply as “amine compound”.

In the above formulas (6) to (12), R ⁵ , p, Y, R, q, R ⁶ , R ⁷ and R ⁸ are defined by the structure of the desired pyridone azo compound. Specifically, since these definitions are the same as those described above, description thereof is omitted here.

  In the above method, the diazotization reaction is not particularly limited and may be performed in the absence of a solvent or in a solvent, but is preferably performed in a solvent. As the solvent that can be used in this case, an acidic solvent is preferably used, and more specifically, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, concentrated sulfuric acid and the like can be mentioned. The said solvent may be used individually or may be used with the form of a 2 or more types of mixture, or may be used with the form of the mixture with other solvents, such as water and methanol. The amount of the solvent used when the solvent is used is not particularly limited, but is an amount such that the concentration of the amine compound is preferably 1 to 40% by weight with respect to the amount of the solvent used. Moreover, it is preferable that an amine compound (preferably solution form) is cooled to about -10-10 degreeC. Thereby, the diazonium produced | generated by subsequent reaction may be stable.

  The diazotization reaction is preferably performed in the presence of a nitrosating agent. Here, the nitrosating agent is not particularly limited, and a known nitrosating agent can be used. Specific examples include nitrosylsulfuric acid, sodium nitrite, methyl nitrite and the like. In addition, the said solvent may be used independently or may be used with the form of 2 or more types of mixtures. The amount of the nitrosating agent used when the nitrosating agent is used is not particularly limited, but is preferably 1.0 to 1.8 mol with respect to 1 mol of the amine compound. The nitrosating agent may be added as it is, but may be diluted with water, methanol or the like. In the latter case, the nitrosating agent is preferably diluted to about 3 to 40% by weight.

  The diazotization reaction conditions are not particularly limited as long as the diazotization reaction of the amine compound proceeds to obtain a desired diazo compound. Specifically, the reaction temperature is preferably −15 to 15 ° C., more preferably −10 to 10 ° C. The reaction time is preferably 1 minute to 10 hours, more preferably 1.5 minutes to 3 hours. Here, the excess nitrosating agent may be decomposed by adding sulfamic acid.

  Next, the diazonium compound thus obtained is subjected to a coupling reaction with the compound (9), the compound (10), the compound (11), or the compound (12).

  Here, the coupling reaction is not particularly limited, and may be performed in the absence of a solvent or in a solvent, but is preferably performed in a solvent. For example, the compound (9), the compound (10), the compound (11), or the compound (12) may be added to the diazo compound in any form, but is preferably added in the form of a solution. Here, the solvent used is not particularly limited as long as it can dissolve or disperse the compound (9), the compound (10), the compound (11), or the compound (12). For example, water, methanol or the like is used. The said solvent may be used independently or may be used with the form of a 2 or more types of mixture. The amount of the solvent used when the solvent is used is not particularly limited, but the concentration of the compound (9), the compound (10), the compound (11), or the compound (12) is preferably 3 to 30% by weight. Is such an amount.

  In consideration of the solubility of the compound (9), the compound (10), the compound (11), or the compound (12), the reactivity of the coupling reaction, etc., the compound (9), the compound (10), (11 The compound or the solution of the compound (12) preferably further contains a base. In this case, examples of the base include sodium hydroxide, sodium carbonate, sodium acetate, potassium hydroxide and the like. The addition amount of the base is not particularly limited, but is 0.9 to 20 mol with respect to 1 mol of (9) compound, (10) compound, (11) compound, or (12) compound.

  The coupling reaction conditions are not particularly limited as long as the reaction with (9) compound, (10) compound, (11) compound, or (12) compound proceeds with the desired pyridone azo compound. Not. Specifically, the reaction temperature is preferably −15 to 15 ° C., more preferably −10 to 10 ° C. Moreover, reaction time becomes like this. Preferably it is 0.1 to 30 minutes, More preferably, it is 0.5 to 20 minutes.

  After completion of the coupling reaction, for example, by filtration, etc., and by performing drying (for example, vacuum drying), a precursor of the pyridone azo compound of the present invention is obtained (in the present specification, simply “ Also referred to as “pyridone azo compound precursor”.

  Finally, a desired silane coupling agent is appropriately selected so that the structure of the desired pyridone azo compound is obtained, and a group derived from the silane coupling agent is introduced into the pyridone azo compound precursor by a conventionally known method. Thus, the pyridone azo compound of the present invention can be produced.

In one embodiment, the resulting pyridone azo compound precursor carboxylic acid (—COOH) or sulfonic acid (—SO ₃ H) is converted to carboxylic acid chloride (—COCl) or sulfonyl chloride (—) using a chlorinating agent. It converted to -SO ₂ Cl) to (chlorination). The chlorination reaction is preferably performed in the presence of a solvent. The solvent used in this case is not particularly limited as long as it can sufficiently dissolve or disperse the pyridone azo compound precursor and the chlorinating agent. In this case, two or more kinds of solvents may be used in combination. Specific examples of the solvent include acetonitrile, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, dimethylformamide, diethyl ether, tetrahydrofuran, dioxane, dichloroethane, chloroform, methanol, ethanol, acetone, and ethylmethyl. Examples include ketone, hexane, benzene, toluene, o-dichlorobenzene and the like. The amount of the solvent used is not particularly limited, but is such an amount that the concentration of the pyridone azo compound precursor is preferably 1 to 30% by weight.

  There is no restriction | limiting in particular in the chlorinating agent used for chlorination reaction, A conventionally well-known chlorinating agent can be selected suitably. Specific examples of the chlorinating agent include thionyl chloride, chlorosulfonic acid, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like, and thionyl chloride is particularly preferable. The amount of the chlorinating agent used is not particularly limited, but is 1 to 8 mol per 1 mol of the pyridone azo compound precursor.

  In the chlorination reaction, the order of adding the pyridone azo compound precursor and the chlorinating agent is not particularly limited. Chlorination reaction conditions are not particularly limited as long as the desired carboxylic acid chloride and sulfonyl chloride can be obtained. Specifically, the reaction temperature is preferably 20 to 100 ° C, more preferably 30 to 90 ° C. Moreover, reaction time becomes like this. Preferably it is 0.5 to 40 hours, More preferably, it is 1 to 24 hours. After completion of the reaction, if necessary, the reaction solution is poured into water to precipitate carboxylic acid chloride and sulfonyl chloride, and the precipitate is separated by filtration. Then, the desired carboxylic acid chloride and sulfonyl chloride can be obtained by drying (especially vacuum drying) the precipitate as necessary.

  Thereafter, the obtained carboxylic acid chloride and sulfonyl chloride are reacted with a silane coupling agent having a desired amine (hereinafter, also referred to as “aminosilane coupling agent”), thereby acid amidation and sulfonamidation. The desired pyridone azo compound is synthesized. The acid amidation and sulfonamidation reaction is preferably performed in the presence of a solvent. The solvent used in this case is not particularly limited as long as it can sufficiently dissolve or disperse carboxylic acid chloride, sulfonyl chloride and aminosilane coupling agent. Specific examples of the solvent include methanol, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, acetonitrile, dimethylformamide, diethyl ether, tetrahydrofuran, dichloroethane, chloroform, ethanol, acetone, ethyl methyl ketone, Hexane, benzene, toluene, o-dichlorobenzene and the like can be mentioned. The amount of the solvent used is not particularly limited, but is such an amount that the concentration of the carboxylic acid chloride or sulfonyl chloride precursor is preferably 1 to 30% by weight.

  When an aminosilane coupling agent is used in the acid amidation or sulfonamidation reaction to obtain a pyridone azo compound represented by the formula (1), formula (1 ′), or formula (2), the amount used thereof is the desired pyridone azo compound. There is no particular limitation as long as the compound is obtained. 1 mol of carboxylic acid chloride or sulfonyl chloride precursor (when there are n carboxylic acid chloride or sulfonyl chloride functional groups per molecule, 1 / n mol of precursor) Where n is an integer of 1 or more), preferably 0.9 to 20 mol, more preferably 1 to 10 mol.

  When an aminosilane coupling agent having two amine sites in the molecule is used in the acid amidation or sulfonamidation reaction for obtaining the pyridone azo compound represented by the formula (2 ′), the amount used thereof is the desired pyridone azo compound. There is no particular limitation as long as the compound is obtained. 1 mol of carboxylic acid chloride or sulfonyl chloride precursor (when there are n carboxylic acid chloride or sulfonyl chloride functional groups per molecule, 1 / n mol of precursor) However, n is an integer of 1 or more), preferably 0.4 to 1.3 mol, more preferably 0.45 to 1.1 mol.

  The acid amidation and sulfonamidation reaction is preferably performed in the presence of a base in order to trap HCl produced as a by-product. The base used in this case is not particularly limited, and specific examples include triethylamine, tripropylamine, triethanolamine, pyridine, potassium carbonate, sodium carbonate, sodium bicarbonate, and the like, and triethylamine is particularly preferable. .

  In the acid amidation and sulfonamidation reactions, the order of addition of the carboxylic acid chloride, sulfonyl chloride precursor and diamine silane coupling agent is not particularly limited. For example, a method of simultaneously adding a carboxylic acid chloride, sulfonyl chloride precursor and a diamine silane coupling agent; a carboxylic acid chloride, sulfonyl chloride precursor is added to a diamine silane coupling agent Method: Any method of adding a diamine silane coupling agent to a carboxylic acid chloride or sulfonyl chloride precursor may be used. Preferably, a diamine silane coupling agent is added (particularly dropwise) to the carboxylic acid chloride or sulfonyl chloride precursor. By adopting such an addition order, the target product can be obtained in good yield.

  The reaction conditions for acid amidation and sulfonamidation are not particularly limited as long as the desired pyridone azo compound can be obtained. Specifically, the reaction temperature is preferably −10 to 40 ° C., more preferably −5 to 30 ° C. Moreover, reaction time becomes like this. Preferably it is 0.01 to 2 hours, More preferably, it is 0.1 to 1 hour. After completion of the reaction, an acid aqueous solution (for example, acetic acid, hydrochloric acid, etc.) is poured into the reaction solution, or the reaction solution is poured into an acid aqueous solution to precipitate a precipitate, and the precipitate is filtered off. Then, the pyridone azo compound of this invention can be obtained by drying a precipitate (especially vacuum drying) as needed.

  When the pyridone azo compound of the present invention (for example, printed matter) is placed under heating, for example, 80 to 100 ° C., 120 to 150 ° C., or 180 to 200 ° C., 100 to 200 hours, 24 to 48 hours, or Even in the case of being heated for 1 to 5 hours, the pyridone azo compound of the present invention has good heat resistance, and thus is not easily sublimated or decomposed.

  Hereinafter, as an application of the pyridone azo compound of the present invention, an inkjet ink will be described as an example. That is, the other form of this invention is the ink for inkjets containing the pyridone azo compound of this 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 pyridone azo 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 pyridone azo 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 ink-jet ink of the present invention must contain the pyridone azo compound of the present invention as a pigment. Here, the blending amount of the pyridone azo compound of the present invention is not particularly limited, but is preferably 1 to 40% by weight, and more preferably 3 to 30% by weight with respect to 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 pyridone azo compound of this invention may be used independently or may be used with the form of 2 or more types of mixtures.

  The ink-jet 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. In addition, the said other pigment or dye may be used independently or may be used with the form of 2 or more types of mixtures.

  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 adhesiveness, 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.

  In addition, the ink jet ink of the above form 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 printability and printed matter resistance. In addition, since these other additives are the same as the above, description is abbreviate | omitted here.

  The ink jet ink of the above form can be produced by a known method. For example, it can be prepared by thoroughly dispersing a dye, a polymerizable monomer, a polymerization initiator, and, if necessary, other additives using a normal dispersing machine such as a sand mill. At this time, a high concentration concentrate of the dye may be prepared in advance and then diluted with a polymerizable monomer. If necessary, the dispersion thus obtained may be filtered with a filter having a pore size 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.

  The pyridone azo compound contained in the inkjet ink of the present invention is excellent in heat resistance. Therefore, even when the ink-jet ink is used for an application in which it is heat-treated after being ejected onto the printing material, the decomposition of the pyridone azo compound can be suppressed, so that discoloration is effectively prevented. be able to. In addition, since the pyridone azo compound contained in the inkjet ink of the present invention is excellent in solvent solubility, a stable dissolved state is maintained in the inkjet ink, and the solvent resistance is improved after polymerization after printing. To do.

  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 (1)>

  After mixing 200 g of methyl cyanoacetate and 136 g of butylamine and stirring at 100 ° C. for 5 hours, 226 g of methyl acetoacetate and then 181 g of piperidine were added dropwise and stirred at 100 ° C. for 5 hours. After cooling the reaction solution to room temperature, the reaction solution was added dropwise to 2000 g of 7.2 wt% hydrochloric acid which was vigorously stirred. The precipitate obtained by filtration was stirred and washed with 400 g of acetone / 600 g of water, filtered and then dried under vacuum to obtain 237 g of compound (a).

  10.0 g of 3-aminobenzoic acid was dissolved in 194 g of 9% by weight hydrochloric acid, and a solution of sodium nitrite 5.53 g in water (11.1 g) was added dropwise at 0 ° C. After stirring for 1 hour, 1.42 g of sulfamic acid was added, and the mixture was further stirred for 5 minutes. Thereafter, a solution obtained by dissolving 15.0 g of the compound (a) in an aqueous sodium hydroxide solution (4.38 g of sodium hydroxide / 164 g of water) was added dropwise to the reaction solution. The precipitate obtained by filtration was washed with stirring with a mixed solution of 100 g of acetone / 300 g of water, filtered and then dried under vacuum to obtain 23.9 g of compound (b).

  18.0 g of compound (b) was suspended in 150 g of 1,4-dioxane, and 18.1 g of thionyl chloride was added at room temperature. The mixture was stirred at 80 ° C. for 3.5 hours, concentrated and then dried under vacuum to obtain 18.6 g of compound (c).

  13.3 g of compound (c) was stirred and suspended in 79.6 g of acetonitrile at 0 ° C. At that temperature, a mixture of 6.71 g of 3-aminopropyltrimethoxysilane and 10.8 g of triethylamine was added dropwise, and the mixture was further stirred for 20 minutes. Further, 221 g of a 10 wt% aqueous acetic acid solution was added dropwise to the reaction solution at that temperature, and the precipitate was immediately collected by filtration. The mixture was vacuum dried by heating to obtain 16.5 g of azo compound (1).

  Example 2 <Synthesis of Compound (2)>

  20.0 g of methyl cyanoacetate and 15.8 g of ethoxyethylamine were mixed and stirred at 100 ° C. for 5 hours. Then, 22.6 g of methyl acetoacetate and then 18.1 g of piperidine were added dropwise and stirred at 100 ° C. for 6 hours. It was. The reaction solution was cooled to room temperature, and then the reaction solution was added dropwise with a dropping funnel to 200 g of 7.2 wt% hydrochloric acid stirred vigorously. The precipitate was collected by filtration and dried in vacuo under heating to obtain 27.2 g of compound (d).

  7.00 g of 3-aminobenzoic acid was dissolved in 136 g of 9 wt% hydrochloric acid, and a solution of 3.87 g of sodium nitrite in water (7.75 g) was added dropwise at 0 ° C. After stirring for 1 hour, 0.99 g of sulfamic acid was added, and the mixture was further stirred for 5 minutes. Thereafter, a solution obtained by dissolving 11.3 g of the compound (d) in an aqueous sodium hydroxide solution (3.06 g of sodium hydroxide / 123 g of water) was added dropwise to the reaction solution. The precipitate obtained by filtration was collected by filtration and dried under vacuum under heating to obtain 17.9 g of compound (e).

  17.9 g of the compound (e) was suspended in 142 g of 1,4-dioxane, and 14.3 g of thionyl chloride was added at room temperature. The mixture was stirred at 80 ° C. for 3 hours, concentrated and then dried under vacuum to obtain 16.2 g of compound (f).

  2.00 g of compound (f) was stirred and suspended in 11.5 g of acetonitrile at 0 ° C. At that temperature, a mixed solution of 0.97 g of 3-aminopropyltrimethoxysilane and 1.56 of triethylamine was added dropwise, and the mixture was further stirred for 5 minutes. The reaction solution was added dropwise to 33 g of a 10% by weight aqueous acetic acid solution, and the precipitate was immediately collected by filtration. The mixture was vacuum dried by heating to obtain 2.33 g of azo compound (2).

  Example 3 <Synthesis of Compound (3)>

  After mixing 100 g of methyl cyanoacetate and 109 g of isopropoxypropylamine and stirring at 80 ° C. for 6.5 hours, 113 g of methyl acetoacetate and then 90.3 g of piperidine were added dropwise and stirred at 80 ° C. for 5.5 hours. It was. The reaction solution was cooled to room temperature, and then the reaction solution was added dropwise with a dropping funnel to 1000 g of 7.2 wt% hydrochloric acid vigorously stirred. The precipitate was washed with stirring with 300 g of methanol / 400 g of water, and then collected by filtration and dried under vacuum under heating to obtain 142 g of compound (g).

  8.00 g of 3-aminobenzoic acid was dissolved in 156 g of 9% by weight hydrochloric acid, and a solution of 4.43 g of sodium nitrite in water (8.86 g) was added dropwise at 0 ° C. After stirring for 40 minutes, 1.13 g of sulfamic acid was added and further stirred for 5 minutes. Thereafter, a solution obtained by dissolving 14.6 g of compound (g) in an aqueous sodium hydroxide solution (sodium hydroxide 3.50 g / water 159 g) was added dropwise to the reaction solution. The precipitate obtained by filtration was washed with stirring with acetone / water. After filtration, the precipitate was heated and dried under vacuum to obtain 16.6 g of compound (l).

  16.6 g of compound (l) was suspended in 123 g of 1,4-dioxane, and 12.4 g of thionyl chloride was added at room temperature. The mixture was stirred at 80 ° C. for 4 hours, concentrated and then vacuum dried under heating to obtain 16.8 g (97 mol%) of compound (m).

  2.00 g of the compound (m) was stirred and suspended in 10.7 g of acetonitrile at 0 ° C. At that temperature, a mixed solution of 0.90 g of 3-aminopropyltrimethoxysilane and 1.46 g of triethylamine was added dropwise, and the mixture was further stirred for 15 minutes. The reaction solution was added dropwise to 33 g of a 10% by weight aqueous acetic acid solution, and the precipitate was immediately collected by filtration. The mixture was vacuum dried by heating to obtain 2.43 g of azo compound (3).

  Example 4 <Synthesis of Compound (4)>

  30.0 g of anthranilic acid was dissolved in 583 g of 9% by weight hydrochloric acid, and a solution of 16.6 g of sodium nitrite in water (33.2 g) was added dropwise at 0 ° C. After stirring for 30 minutes, 4.25 g of sulfamic acid was added and further stirred for 5 minutes. Thereafter, a solution obtained by dissolving 45.1 g of the compound (a) in a sodium hydroxide aqueous solution (sodium hydroxide 13.1 g / water 491 g) was added dropwise to the reaction solution. The precipitate obtained by filtration was stirred and washed with methanol, collected by filtration, and dried under vacuum under heating to obtain 75.5 g of compound (p).

  25.0 g of the compound (p) was suspended in 208 g of 1,4-dioxane, and 21.0 g of thionyl chloride was added at room temperature. The mixture was stirred at 80 ° C. for 6 hours, concentrated and then dried under vacuum to obtain 26.3 g of compound (q).

  2.00 g of compound (q) was stirred and suspended in 12.0 g of acetonitrile at 0 ° C. At that temperature, a mixed solution of 1.25 g of 3-aminopropyltriethoxysilane and 1.63 g of triethylamine was dropped, and the mixture was further stirred for 15 minutes. The reaction solution was added dropwise to 33 g of a 10% by weight aqueous acetic acid solution, and the precipitate was immediately collected by filtration. Heating and vacuum drying were performed to obtain 2.16 g of an azo compound (4).

  Example 5 <Synthesis of Compound (5)>

  150 g of methyl cyanoacetate and 82.3 g of propylamine were mixed, stirred at 50 ° C. for 6 hours, and then stirred at 100 ° C. for 3 hours. Thereafter, 169 g of methyl acetoacetate and then 136 g of piperidine were added dropwise and stirred at 100 ° C. for 4.5 hours. After cooling the reaction solution to room temperature, the reaction solution was added dropwise to 1500 g of 7.2 wt% hydrochloric acid that was vigorously stirred. The precipitate obtained by filtration was stirred and washed with 500 g of acetone, filtered and then dried under vacuum to obtain 119 g of compound (r).

  After 37.0 g of sulfanilic acid was dissolved in a mixed solution of 150 g of water and 32.0 g of concentrated hydrochloric acid, 25.0 g of 4N sodium nitrite was added dropwise at 5 to 10 ° C., and the mixture was stirred at that temperature for 1 hour.

  Next, 370 g of water was added to 38.9 g of compound (r), and a solution prepared to pH 8 with 2N sodium hydroxide was added to the coupling component while maintaining the temperature at 10 ° C. or lower. The pH is adjusted to 5.0 with sodium hydroxide to complete the coupling reaction. After the reaction is completed, salting out is performed using 100 g of sodium chloride, and the precipitated product is separated by filtration and heated and vacuum-dried. 61.0 g of the compound (s) was obtained.

  10 g of the compound (s) was suspended in a mixed solution of 59 g of acetonitrile and 4 g of DMF, and 7 g of thionyl chloride was added at room temperature. After stirring at 40 ° C. for 4 hours and cooling to room temperature, the reaction solution was poured into 100 g of water. The precipitate was collected by filtration and dried in a vacuum under heating to obtain 7.6 g of compound (t).

  4 g of compound (t) was stirred and suspended in 30 g of dioxane at 5 ° C. At that temperature, a mixed solution of 2.2 g of 3-aminopropyltriethoxysilane and 3.7 g of triethylamine was dropped, and the mixture was further stirred for 5 minutes. The reaction solution was added dropwise to 38 g of a 5 wt% aqueous acetic acid solution, and the precipitate was immediately collected by filtration. Heating and vacuum drying were performed to obtain 5 g of an azo compound (5).

  Example 6 <Synthesis of Compound (6)>

  After 37.0 g of sulfanilic acid was dissolved in a mixed solution of 150 g of water and 32.0 g of concentrated hydrochloric acid, 25.0 g of 4N sodium nitrite was added dropwise at 5 to 10 ° C., and the mixture was stirred at that temperature for 1 hour. Next, 370 g of water was added to 41.7 g of compound (a), and a solution prepared to pH 8 with 2N sodium hydroxide was added to the coupling component while maintaining the temperature at 10 ° C. or lower. The pH is adjusted to 5.0 with sodium hydroxide to complete the coupling reaction. After the reaction is completed, salting out is performed using 100 g of sodium chloride, and the precipitated product is separated by filtration and heated and vacuum-dried. As a result, 70.6 g of the compound (u) was obtained.

  50.0 g of the compound (u) was suspended in a mixed solution of 296 g of acetonitrile and 19 g of DMF, and 39.5 g of thionyl chloride was added at room temperature. After stirring at 40 ° C. for 5 hours and cooling to room temperature, the reaction solution was poured into 444 g of water. The precipitate was collected by filtration and then dried under vacuum under heating to obtain 43.8 g of compound (v).

  The compound (v) (3.00 g) was suspended in 19.1 g of acetonitrile at 0 ° C. by stirring. At that temperature, a mixed solution of 1.71 g of 3-aminopropyltriethoxysilane and 2.23 g of triethylamine was dropped, and the mixture was further stirred for 5 minutes. The reaction solution was added dropwise to 50 g of a 10% by weight acetic acid aqueous solution, and the precipitate was immediately collected by filtration. The mixture was vacuum dried by heating to obtain 3.76 g of azo compound (6).

Example 7 <Polymerization reaction>
0.62 g of the compound (1) was suspended in a mixed solvent of 6.2 g of acetone and 3.1 g of water and stirred at room temperature for 3 hours. Water was added to sufficiently precipitate the sample, which was collected by filtration and dried in a vacuum under heating to obtain azo compound (1) ′ in which compound (1) was polymerized.

Example 8 <Polymerization reaction>
1.00 g of compound (2) was suspended in a mixed solvent of 10.0 g of acetone and 5.0 g of 3.6% by weight hydrochloric acid, and stirred at room temperature for 3 hours. Water was added to sufficiently precipitate the sample, which was collected by filtration and dried in a vacuum under heating to obtain azo compound (2) ′ in which compound (2) was polymerized.

Examples 9 to 12 <Polymerization reaction>
The compounds (3) to (6) were respectively subjected to the same operations as in Example (8) to obtain azo compounds (3) ′ to (6) ′.

  Comparative Example 1 <Synthesis of Compound (7)>

  After 37.0 g of sulfanilic acid was sufficiently stirred with 150 g of water and 32.0 g of concentrated hydrochloric acid, it was diazotized at 5 to 10 ° C. with 25.0 g of 4N sodium nitrite and then 1-ethyl-1,2-dihydro- 370 g of water was added to 42.0 g of 6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile, and a solution adjusted to pH 8 with 2N sodium hydroxide was kept at a temperature of 10 ° C. or less in the coupling component. And added. The pH is adjusted to 5.0 with sodium hydroxide to complete the coupling reaction. After completion of the reaction, 100 g of sodium chloride is used for salting out, and the precipitated product is filtered off and vacuum dried at 60 ° C. 60.4 g of the compound (d) represented was obtained.

  While 35.0 g of the compound (d) was suspended in a mixed solvent of 15.6 g of dimethylformamide and 215.5 g of acetonitrile under ice-cooling, thionyl chloride was added dropwise. After a while, the temperature was raised to 40 ° C. and further stirred for 4 hours. Thereafter, the suspension was poured into 525 g of water while stirring, and further stirred for 10 minutes. The resulting precipitate was collected by filtration and dried in vacuo at 60 ° C. to obtain 29.2 g of a sulfonic acid chloride (e).

29.2 g of sulfonic acid chloride (e) was suspended in chloroform under ice cooling, and a mixed solution of 14.9 g of 2-ethylhexylamine and 38.9 g of triethylamine was slowly added dropwise. After warming to room temperature and stirring for 10 minutes, the reaction solution was concentrated. The concentrate was dissolved in 150 g of acetone, poured into 600 parts of 1M hydrochloric acid, and the resulting precipitate was collected by filtration. This precipitate was dissolved in 400 g of methanol under heating and refluxing, and slowly cooled to room temperature. The resulting precipitate was collected by filtration and then vacuum dried at 60 ° C. to obtain 28.4 g of Compound (7).
Using the azo compounds obtained in Examples 1 to 6, Examples 7 to 12, and Comparative Example 1, Gram extinction coefficient, solubility test, and sublimation test were performed. The results are summarized in Table 1.

<Measurement of Gram extinction coefficient>
A solution of 30 mg of the obtained azo compound in ethyl acetate was diluted to 50 mL in a volumetric flask to prepare a 0.6 g / L solution. Then, 1 mL was taken out from the prepared solution with a whole pipette, and diluted to 50 mL with ethyl acetate in a volumetric flask to prepare a 0.012 g / L solution. The solution thus prepared was put into 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). The absorbance ε (g) per gram at the maximum absorbance was calculated by the following formula.

<Solubility test>
30 mg of the obtained azo compound was placed in a vial, cyclohexanone (CHN) was added at room temperature (20 ° C.), and the weight of the minimum amount of CHN required to dissolve the azo compound was determined. The concentration (wt%) of the azo compound in the calculated CHN weight was calculated and used as the solubility (solubility).

<Sublimation test>
30 mg of the azo compound was weighed into a petri dish having an inner diameter of 28 mm and a height of 15 mm, covered and heated on a hot plate at 230 ° C. for 2 hours. Thereafter, the compound adhering to the petri dish lid was dissolved in 3 mL of cyclohexanone, 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). The absorbance value at 420 nm was determined.

  As for the compounds of Examples 1 to 6, the sublimation product has an absorbance value at 420 nm that is clearly less than that of the comparative compound of Comparative Example 1. When an alkoxysilyl group is introduced, an effect of suppressing the sublimation by partial progress of polymerization due to heating is recognized. Although the compound of Examples 7-12 is a compound which polymerized the compound of Examples 1-6 intentionally, sublimation is further suppressed compared with Examples 1-10. The compound of the present invention is excellent in sublimation and has solubility in CHN.

Claims (3)

Formula (1) or the formula (2), peak Ridon'azo compounds:
In the above formula (1 ) and formula (2 ) ,
X represents the following formula (3):
A group represented by:
Each Y is independently —CO— or —SO ₂ —;
R ¹ is hydrogen atom;
Each R ² is independently a linear or branched alkylene group having 1 to 6 carbon atoms;
Each R ³ is independently a linear or branched alkyl group having 1 to 4 carbon atoms;
p is 1 ;
Each R ⁶ is independently a linear or branched alkyl group having 1 to 3 carbon atoms;
R ⁷ is a straight-chain or straight-chain alkyl group or a C 3-14 branched chain or branched alkoxyalkyl group having 3 to 10 carbon atoms;
R ⁸ is a linear or branched alkylene group having 1 to 12 carbon atoms, or the following formula (5)
:
In this case, each R ⁹ is independently a linear or branched alkylene group having 1 to 12 carbon atoms; and n represents an integer of 1 to 8. The pyridone azo compound according to claim 1, which is represented by any one of the following formulas.
An inkjet ink comprising the pyridone azo compound according to claim 1.