JP2005225944A - Inkjet ink and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet ink for obtaining inkjet prints, which excels in both light resistance and oxidizing gas resistance, particularly has strong ozone resistance, and reduces occurrence of uneven discoloration and fading, and an inkjet recording method. <P>SOLUTION: The inkjet ink comprises at least one kind of the dyes represented by formulae (1) to (14) and a resin component. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an inkjet ink and an inkjet recording method.

  In recent years, the progress of ink jet technology has been remarkable, and it has come to be called photo image quality in combination with improvements in printer technology, ink technology, and dedicated recording medium technology. With the improvement in image quality, the storability of inkjet images has been compared with conventional silver salt photographs, and in particular, weakness in fading such as light resistance and oxidation resistance gas resistance has been pointed out in dye ink printing.

  Many studies have been made to improve fading, but it is still insufficient in comparison with silver salt prints. Many efforts have been made to improve the fastness of the dye itself for the purpose of improving fading, but it is still insufficient. In particular, the magenta dye has a relatively weak fading property.

  Up to now, azo dyes mainly using H acid have been widely used, but light resistance and oxidation resistance gas resistance (ozone gas resistance etc.) are very weak, and it can be viewed and stored by sticking a print sample on the wall. It was a level that I could not bear.

  Patent Document 1, JP-A-11-29714, JP-A-2000-109464, 2000-191660, 2000-256687, 2001-72884, 2001-139636, 2001-288091, 2002 -332418, 2002-332419, 2003-55589, 2003-192930, etc. Some of the anthrapyridone dyes have improved light resistance and ozone gas resistance, but they are still satisfactory. Not a level.

  Patent Document 2, JP-A Nos. 2002-309116 and 2002-371079 disclose heterocyclic-heterocyclic azo dyes, which are not satisfactory. Especially light resistance is weak.

  Patent Document 3, JP-A Nos. 2003-335990, 2003-342504, and 2003-335899 disclose novel dyes such as pyridone-based dyes, but at levels that are still satisfactory in both light resistance and ozone gas resistance. Absent.

  Japanese Patent Application Laid-Open Nos. 2002-285049 and 2003-55586 disclose a technique for improving ozone resistance by adding polymer latex or resin fine particles to ink. However, the level is insufficient because it causes a decrease in gloss of the print, greatly reduces the ink absorption rate, and further causes ozone fading unevenness.

Accordingly, there is a demand for an ink jet print having sufficient light resistance and oxidation gas resistance comparable to silver salt print, high gloss, and improved generation of ozone fading unevenness, and an ink and a recording method for realizing the same. It is rare.
JP-A-10-306221 JP 2002-309115 A JP 2003-342500 A JP 2002-240413 A

  The present invention has been made in view of the above problems, and provides an ink-jet ink and an ink-jet recording method for obtaining an ink-jet print excellent in both light resistance and oxidation-resistant gas resistance, particularly strong in ozone resistance, and with little occurrence of fading unevenness. There is to do.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
An ink-jet ink comprising at least one dye represented by the following general formulas (1) to (14) and a resin component.

(Wherein R ₁₁ represents a branched alkyl group, a cycloalkyl group, a heterocyclic group or an amino group, R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom or a substituent, and n11 represents an integer of 1 to 3. N12 represents an integer of 1 to 4.)

(In the formula, R ₂₁ represents a heterocyclic group, R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom or a substituent, n ₂₁ represents an integer of 1 to 3, and n ₂₂ represents an integer of 1 to 4. )

(Wherein R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ each represent a hydrogen atom or a substituent, and n ₃₁ represents an integer of 1 to 3)

Wherein R ₄₁ , R ₄₂ and R ₄₃ each represent a hydrogen atom or a substituent, n41 represents an integer of 1 to 3, and Z forms a 5- to 7-membered heterocyclic group together with the carbon atom. Represents a group of non-metallic atoms necessary for

(In the formula, R ₅₁ , R ₅₂ , and R ₅₃ each represent a hydrogen atom or a substituent, n51 represents an integer of 1 to 3, and n52 represents an integer of 1 to 4.)

(In the formula, R ₆₁ , R ₆₂ , R ₆₃ , and R ₆₄ each represent a hydrogen atom or a substituent, and n ₆₁ represents an integer of 1 to 3)

(Wherein R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ each represents a hydrogen atom or a substituent, and n71 represents an integer of 1 to 3)

(In the formula, R ₈₁ , R ₈₂ and R ₈₃ each independently represents a hydrogen atom or a substituent, n81 represents an integer of 1 to 3, and n82 represents an integer of 1 or 2.)

(In the formula, R ₉₁ , R ₉₂ , R ₉₃ and R ₉₄ each independently represents a hydrogen atom or a substituent, n91 represents an integer of 1 to 3, and n92 represents an integer of 1 or 2.)

(Wherein R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ each independently represents a hydrogen atom or a substituent, and n ₁₀₁ represents an integer of 1 to 3)

(In the formula, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ each independently represents a hydrogen atom or a substituent, and n ₁₁₁ represents an integer of 1 to 3.)

(Wherein R ₁₂₁ , R ₁₂₂ , R ₁₂₃ , R ₁₂₄ and R ₁₂₅ each independently represent a hydrogen atom or a substituent, and n121 represents an integer of 1 to 3)

(In the formula, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ , and R ₁₃₄ each independently represent a hydrogen atom or a substituent, n131 represents an integer of 1 to 3, and n132 represents an integer of 1 or 2.)

(In the formula, R ₁₄₁ , R ₁₄₂ , R ₁₄₃ and R ₁₄₄ each independently represent a hydrogen atom or a substituent, n141 represents an integer of 1 to 3, and n142 represents an integer of 1 to 4).
(Claim 2)
The inkjet ink according to claim 1, wherein the resin component is resin fine particles.

(Claim 3)
3. An ink jet recording method comprising: recording on a void type ink jet recording medium using the ink jet ink according to claim 1.

(Claim 4)
The inkjet recording method according to claim 3, wherein the 60 ° specular gloss of the void-type inkjet recording medium is 40% or more.

  According to the present invention, it is possible to provide an ink jet ink and an ink jet recording method for obtaining an ink jet print which is excellent in both light resistance and oxidation resistance gas resistance, particularly strong in ozone resistance, and causes less discoloration unevenness.

  As a result of diligent research, the inventor of the present invention is excellent in both light resistance and oxidation resistance gas resistance due to the inkjet ink containing at least one dye represented by the general formulas (1) to (14) and a resin component. It has been found that an ink-jet ink for obtaining an ink-jet print having strong ozone resistance and less discoloration unevenness can be obtained.

  The present invention will be described in detail below.

Next, the inkjet ink of the present invention (hereinafter also simply referred to as ink) will be described.
The ink of the present invention contains at least one dye represented by the general formulas (1) to (14) and a resin component.

(Dyes represented by general formulas (1) to (4))
First, the compound represented by the general formula (1) will be described.

In the general formula (1), R ₁₁ represents a branched alkyl group (for example, isopropyl group, t-butyl group, 2-ethylhexyl group, etc.), a cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, etc.), a heterocyclic group (for example, 2-pyridyl group, 4-pyridyl group, 2-pyrrole group and the like) and amino group (for example, butylamino group, anilino group, morpholino group and the like).

R ₁₁ may have a substituent, and these substituents are not particularly limited, but typically, alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, etc. In addition to these, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, sulfonyloxy Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, Rubokishi, hydroxy, mercapto, nitro, each group such as sulfo, and a spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned.

R ₁₁ is preferably a branched alkyl group or an amino group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

R ₁₂ represents a hydrogen atom or a substituent, and the substituent is not particularly limited, and representative examples thereof include alkyl, aryl, alkenyl, cycloalkyl and the like, but cycloalkenyl, alkynyl, Examples thereof include a ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, alkoxy, aryloxy, heterocyclic oxy, siloxy, alkoxycarbonyl, aryloxycarbonyl and the like.

R ₁₃ and R ₁₄ each represent a hydrogen atom or a substituent. The substituent is not particularly limited, but representative examples thereof include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, and the like. Cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, Sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto Nitro, each group such as sulfo, and a spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned.

In the general formula (1), n11 represents an integer of 1 to 3, n12 represents an integer of 1 to 4, and when n11 and n12 are 2 or more, R ₁₃ and R ₁₄ may be the same or different.

  Next, the compound represented by the general formula (2) will be described.

In the general formula (2), R ₂₁ represents a heterocyclic group, and examples thereof include a 2-pyridyl group, a 4-pyridyl group, a 2-furyl group, and a 2-thienyl group.

R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom or a substituent, and examples of the substituent represented by R ₂₂ include the same substituents as R ₁₂ in the general formula (1). Further, examples of the substituents represented by R _23, R ₂₄ may include the same substituent as R _13, R ₁₄ in the general formula (1).

n21 represents an integer of 1 to 3, n22 represents an integer of 1 to 4, and when n21 and n22 are 2 or more, R ₂₃ and R ₂₄ may be the same or different.

  Next, the compound represented by the general formula (3) will be described.

In the general formula (3), R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ each represent a hydrogen atom or a substituent. Examples of the substituent represented by R ₃₂ include those in the general formula (1). The same substituents as R ₁₂ can be mentioned. Further, examples of the substituents represented by _{R 31, R 33, R 34} , R 35 may include the same substituent as R _13, R ₁₄ in the general formula (1).

n31 represents an integer of 1 to 3, and when n31 is 2 or more, R ₃₃ may be the same or different. R ₃₄ and R ₃₅ may be bonded to each other to form a ring.

  Next, the compound represented by the general formula (4) will be described.

In the general formula (4), R ₄₁ , R ₄₂ and R ₄₃ each represent a hydrogen atom or a substituent. Examples of the substituent include the same substituents as R ₁₃ and R ₁₄ in the general formula (1) The group can be mentioned.

  Z represents a nonmetallic atom group that forms a 5- to 7-membered heterocyclic group together with a carbon atom, and the 5- to 7-membered heterocyclic group may further have a substituent.

  The 5- to 7-membered heterocyclic group formed by Z together with the carbon atom is preferably a 5- to 6-membered nitrogen-containing heterocyclic ring, and particularly preferably a pyridine ring.

  Specific examples of the compound represented by the general formula (1), (2), (3) or (4) of the present invention are shown below, but the present invention is not limited thereto.

  In the following structural formula, M represents a cation such as sodium salt, potassium salt, ½ calcium salt, or ammonium salt.

  Below, the synthesis example of the exemplary compound 1-4 represented by General formula (1) of this invention is shown. Other compounds represented by the general formula (1) and compounds represented by the general formula (2), (3) or (4) can be synthesized in the same manner.

  Exemplified compound 1-4 was synthesized according to the following scheme (1).

(Synthesis of Intermediate 1c)
32.8 g (0.1 mol) of (1a), 19.0 g (0.12 mol) of (1b) and 1.06 g (0.01 mol) of sodium carbonate were heated to about 140 ° C. in 150 ml of xylene to form The reaction was carried out for 10 hours while distilling off methanol and water. After completion of the reaction, the mixture was cooled, and the precipitated crystals were collected by filtration and washed with cooled 80% ethanol water to obtain 35.8 g (82% yield) of intermediate (1c).

(Synthesis of Exemplified Compound 1-4)
To 73 g of 10% by mass fuming sulfuric acid, 8.73 g (0.02 mol) of intermediate 1c was added at 20 ° C. or lower under ice cooling, and sulfonation was performed at about 50 ° C. for 5 hours. After completion of the reaction, the reaction solution is added to 400 ml of ice water, and further 30 g of sodium chloride is added for salting out, followed by filtration and drying to obtain 10.9 g of sodium salt of Exemplary Compound 1-4 (yield 85%). Obtained.

^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound was the target exemplified compound 1-4.

(Dyes represented by general formulas (5) to (7))
Next, the compound represented by the general formula (5) will be described.

In the general formula (5), R ₅₁ represents a hydrogen atom or a substituent, and the substituent is not particularly limited, and representative examples thereof include alkyl, aryl, alkenyl, cycloalkyl, and the like. Further, each group such as cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, alkoxy, aryloxy, heterocyclic oxy, siloxy, alkoxycarbonyl, aryloxycarbonyl and the like can be mentioned.

R ₅₂ and R ₅₃ represent a hydrogen atom or a substituent. The substituent is not particularly limited, but representative examples include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, and the like. Cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, Sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercap , Nitro, each group such as sulfo, and a spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned.

In General formula (5), n51 represents the integer of 1-3, n52 represents the integer of 1-4. When n51 and n52 is 2 or more, or different, even R ₅₂ and R ₅₃ are respectively the same, and when n51 and n52 is 2 or more, the two R ₅₁ or R ₅₂ bond to each other ring May be formed.

  Next, the compound represented by the general formula (6) will be described.

In the general formula (6), R ₆₁ , R ₆₂ , R ₆₃ and R ₆₄ each represent a hydrogen atom or a substituent. Examples of the substituents representing these include R ₅₂ , R ₅₃ in the general formula (5) and Similar substituents can be mentioned. R ₆₃ and R ₆₄ may be bonded to each other to form a ring.

In R _63, R _64, preferably is preferably form an aromatic ring bonded R _63, R ₆₄ to each other, more preferably, attached R _63, R ₆₄ are each other substituted or unsubstituted benzene It is preferable to form a ring.

In the general formula (6), n61 represents an integer of 1 to 3, when n61 is 2 or more, when R ₆₂ may be different even in the same, also n61 is 2 or more, two R ₆₂ May be bonded to each other to form a ring.

  Next, the compound represented by the general formula (7) will be described.

In the general formula (7), R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ represent a hydrogen atom or a substituent, and examples of the substituent are the same as those of R ₅₂ and R ₅₃ in the general formula (5). A substituent can be mentioned. R ₇₃ and R ₇₄ may be bonded to each other to form a ring.

In R _73, R _74, preferably is preferably form an aromatic ring bonded R _73, R ₇₄ to each other, more preferably, attached R _73, R ₇₄ are each other substituted or unsubstituted benzene It is preferable to form a ring.

In the general formula (7), n71 represents an integer of 1 to 3, when n71 is 2 or more, R ₇₂ may be different even in the same, and when n71 is 2 or more, two R ₇₂ May be bonded to each other to form a ring.

  Specific examples of the compound represented by the general formula (5), (6) or (7) of the present invention are shown below, but the present invention is not limited thereto.

  In the following structural formula, M represents a cation such as sodium salt, potassium salt, 1/2 calcium salt, or ammonium salt.

  Below, the synthesis example of exemplary compound 5-1 represented by General formula (5) of this invention is shown. Other compounds represented by the general formula (5) and compounds represented by the general formula (6) or (7) can be synthesized in the same manner.

  Exemplary compound 5-1 was synthesized according to the following scheme (5).

(Synthesis of Intermediate 5c)
31.4 g (0.1 mol) of (5a) and 12.1 g (0.2 mol) of (5b) were heated to about 140 ° C. in 100 ml of phenol and reacted for 6 hours. After the completion of the reaction, the cooled crystals were collected by filtration and washed with cooled ethanol to obtain 26.5 g of intermediate (5c) (yield 78%).

(Synthesis of Exemplary Compound 5-1)
6.8 g (0.02 mol) of intermediate (5c) was added to 120 g of concentrated sulfuric acid under ice cooling, and sulfonation was performed at 10 ° C. or less for 1 hour. After completion of the reaction, the reaction solution was added to 400 g of ice, and the resulting crystals were filtered. The crystals were added to 5% brine containing a small amount of sodium hydroxide and stirred for 30 minutes, and the crystals were collected by filtration to obtain 7.8 g (yield 72%) of the sodium salt of Example Compound 5-1. It was.

^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound was the target exemplified compound 5-1.

(Dyes represented by general formulas (8) to (11))
Next, the compound represented by the general formula (8) will be described.

In the general formula (8), R ₈₁ , R ₈₂ and R ₈₃ each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but representative examples include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, and the like. Cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, Sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercap , Nitro, each group such as sulfo, and a spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned.

In General formula (8), n81 represents the integer of 1-3, n82 represents the integer of 1-2. When n81 and n82 are 2 or more, R ₈₂ and R ₈₃ may be the same or different. When n81 and n82 are 2 or more, two R ₈₂ or R ₈₃ are bonded to each other to form a ring. May be formed.

  Next, the compound represented by the general formula (9) will be described.

In the general formula (9), R ₉₁ , R ₉₂ , R ₉₃ and R ₉₄ each independently represent a hydrogen atom or a substituent. Examples of the substituent include R ₈₁ , R ₈₂ in the general formula (8). , And the same substituents as R ₈₃ can be exemplified.

In General formula (9), n91 represents the integer of 1-3, n92 represents the integer of 1-2. When n91 and n92 are 2 or more, R ₉₃ and R ₉₄ may be the same or different. When n91 and n92 are 2 or more, two R ₉₃ or R ₉₄ are bonded to each other to form a ring. May be formed.

  Next, the compound represented by General formula (10) is demonstrated.

In the general formula (10), R ₁₀₁ represents a hydrogen atom or a substituent, and the substituent is not particularly limited, but typically includes groups such as alkyl, aryl, alkenyl, cycloalkyl, and the like. Further examples include groups such as cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, alkoxy, aryloxy, heterocyclic oxy, siloxy, alkoxycarbonyl, aryloxycarbonyl and the like.

R ₁₀₂ , R ₁₀₃ and R ₁₀₄ each independently represent a hydrogen atom or a substituent, and examples of the substituent include the same substituents as R ₈₁ , R ₈₂ and R ₈₃ in formula (8). be able to.

In General formula (10), n101 represents the integer of 1-3. When n is 2 or more, R ₁₀₂ may be the same or different, and when n101 is 2 or more, two R ₁₀₂ may be bonded to each other to form a ring.

In the general formula (10), R ₁₀₃ and R ₁₀₄ are preferably bonded to each other to form an aromatic ring, and R ₁₀₃ and R ₁₀₄ are bonded to each other to form a substituted or unsubstituted benzene ring. It is preferable to form.

  Next, the compound represented by General formula (11) is demonstrated.

In the general formula (11), R ₁₁₁ , R ₁₁₂ , and R ₁₁₃ each independently represent a hydrogen atom or a substituent. Examples of the substituent include R ₈₁ , R ₈₂ , R in the general formula (8). The same substituents as ₈₃ can be mentioned.

In General formula (11), n111 represents the integer of 1-3. When n is 2 or more, R ₁₁₁ may be the same or different, and when n ₁₁₁ is 2 or more, two R _112s may be bonded to each other to form a ring.

In general formula (11), R ₁₁₂ and R ₁₁₃ are preferably bonded to each other to form an aromatic ring, and R ₁₁₂ and R ₁₁₃ are preferably bonded to each other to form a substituted or unsubstituted benzene ring. It is preferable to form.

  Specific examples of the compound represented by the general formula (8), (9), (10) or (11) of the present invention are shown below, but the present invention is not limited thereto. Note that M in the structural formula represents a cation such as sodium salt, potassium salt, 1/2 calcium salt, or ammonium salt.

  Below, the synthesis example of exemplary compound 10-13 represented by General formula (10) of this invention is shown. Other compounds represented by the general formula (10) and compounds represented by the general formula (8), (9) or (11) can be synthesized in the same manner.

  Exemplified compounds 10-13 were synthesized according to scheme (10).

(Synthesis of Intermediate 10b)
From 31.3 g (0.1 mol) of (10a) Chem. (10b) was synthesized according to the method described in Soc, 1894-1901 (1954), and 20.8 g (yield 64%) of (10b) was isolated by column chromatography.

(Synthesis of Exemplified Compound 10-13)
6.4 g (0.02 mol) of intermediate (10b) was added to 120 g of concentrated sulfuric acid under ice cooling, and sulfonation was performed at 10 ° C. or less for 1 hour. After completion of the reaction, the reaction solution was added to 400 g of ice, and the resulting crystals were filtered. The crystals were added to 5% brine containing a small amount of sodium hydroxide and stirred for 30 minutes, and the crystals were collected by filtration to obtain 7.8 g (yield 74%) of the sodium salt of Exemplified Compound 10-13. It was.

  From the 1H NMR spectrum, it was confirmed that the obtained compound was the target Exemplified Compound 10-13.

(Dyes represented by general formulas (12) to (14))
Next, the compound represented by General formula (12) is demonstrated.

In the general formula (12), R ₁₂₁ , R ₁₂₂ , R ₁₂₃ , R ₁₂₄ , and R ₁₂₅ each independently represent a hydrogen atom or a substituent. The substituent is not particularly limited, but representative examples include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, and the like. Cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, Sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercap , Nitro, each group such as sulfo, and a spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned. R ₁₂₄ and R ₁₂₅ may be bonded to each other to form a ring.

In R _124, R _125, preferably is preferably form an aromatic ring bonded R _124, R ₁₂₅ to each other, further, R _124, R ₁₂₅ are bonded to a substituted or unsubstituted with one another benzene ring It is preferable to form.

In General formula (12), n121 represents the integer of 1-3. n121 is 2 or more, R ₁₂₃ may be different even in the same, also when n121 is 2 or more, two R ₁₂₃ may be bonded to each other to form a ring.

Next, the compound represented by General formula (13) is demonstrated. In the general formula (13), R ₁₃₁ , R ₁₃₂ , R ₁₃₃ , and R ₁₃₄ each independently represent a hydrogen atom or a substituent. Examples of the substituent include R _{121 to} R ₁₂₅ in the general formula (12) Similar substituents can be mentioned.

In General formula (13), n131 represents the integer of 1-3, n132 represents the integer of 1-4. n131, n132 is 2 or more, R _133, R ₁₃₄ may be different even in the same, also when n131 and n132 is 2 or more, the ring two R ₁₃₃ or R ₁₃₄ are bonded to each other May be formed.

  Next, the compound represented by General formula (14) is demonstrated.

In the general formula (14), R ₁₄₁ , R ₁₄₂ , R ₁₄₃ and R ₁₄₄ each independently represents a hydrogen atom or a substituent. Examples of the substituent include R _{121 to} R in the general formula (12). The same substituents as ₁₂₅ can be mentioned.

In General formula (14), n141 represents the integer of 1-3, n142 represents the integer of 1-4. When n141 and n142 are 2 or more, R ₁₄₃ and R ₁₄₄ may be the same or different. When n141 and n142 are 2 or more, two R ₁₄₃ or R ₁₄₄ are bonded to each other to form a ring. May be formed.

  Specific examples of the compound represented by the general formula (12), (13) or (14) of the present invention are shown below, but the present invention is not limited thereto. Note that M in the structural formula represents a cation such as sodium salt, potassium salt, 1/2 calcium salt, or ammonium salt.

  Below, the synthesis example of the exemplary compound 12-2 represented by General formula (12) of this invention is shown. Other compounds represented by the general formula (12) and the compounds represented by the general formula (13) or (14) can be synthesized in the same manner.

  Exemplified Compound 12-2 was synthesized according to Scheme (12).

(Synthesis of Intermediate 12b)
27.6 g (0.1 mol) of (12a) (synthesized from o-nitrobenzoic acid according to the method described in Synthesis, 2,262-266 (2001), total yield 48%) was dissolved in 150 ml of acetic acid, After adding 25.4g (0.46mol), it reacted at 75 degreeC for 4 hours. After completion of the reaction, the mixture was filtered, the filtrate was extracted with toluene / water, and the solvent was distilled off to obtain an intermediate (12b).

(Synthesis of Intermediate 12c)
(12b) obtained from the above reaction, 15.7 g (0.1 mol) of bromobenzene, 24.6 g (0.3 mol) of sodium acetate and 3.4 g of cuprous chloride were added at about 200 ° C. in 300 ml of nitrobenzene. And reacted for 14 hours. After completion of the reaction, the mixture was cooled, and the precipitated crystals were collected by filtration. The crystals were washed with nitrobenzene, dilute hydrochloric acid, and ethanol to obtain 21.3 g (yield 66%) of (12c).

(Synthesis of Exemplified Compound 12-2)
6.4 g (0.02 mol) of intermediate (12c) was added to 120 g of concentrated sulfuric acid under ice cooling, and sulfonation was performed at 10 ° C. or less for 1 hour. After completion of the reaction, the reaction solution was added to 400 g of ice, and the resulting crystals were filtered. The crystals were added to 5% brine containing a small amount of sodium hydroxide and stirred for 30 minutes, and the crystals were collected by filtration to obtain 8.1 g (yield 78%) of the sodium salt of Example Compound 12-2. It was.

  From the 1H NMR spectrum, it was confirmed that the obtained compound was the target exemplified compound 12-2.

(Resin component)
The resin component only needs to form a resin film on the print, and a water-soluble resin and resin fine particles are used. From the viewpoint of fading improvement and image gloss improvement, the dyes represented by the general formulas (1) to (14) and the resin component are preferably separated in the ink. As described in JP-A Nos. 2003-342500, 2003-335990, 2003-342504, and 2003-335899, a type in which both a dye and an oily polymer are finely dispersed is not preferable. One preferred form of the invention is:
(1) An ink containing at least one water-soluble dye represented by the general formulas (1) to (14) and a water-soluble resin component.
Furthermore, the preferred form is
(2) An ink containing at least one water-soluble dye represented by the general formulas (1) to (14) and resin fine particles. Resin fine particles are more preferable than water-soluble resins from the viewpoints of glossiness, ink absorbability, and ink ejection properties.

(Water-soluble resin)
Water-soluble resins include polyethylene glycol, polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyurethane, dextran, dextrin, color ginan (κ, ι, λ, etc.), agar, pullulan, water-soluble polyvinyl Examples include butyral, hydroxyethyl cellulose, carboxymethyl cellulose, and the like.

(Resin fine particles)
The resin fine particles are also called polymer fine particles or latex, and the resin fine particles can be used in the form of an aqueous dispersion of various resins. Specifically, acrylic, styrene-acrylic, acrylonitrile-acrylic, vinyl acetate, vinyl acetate-acrylic, vinyl acetate-vinyl chloride, polyurethane, silicon-acrylic, acrylic silicon, polyester, Epoxy resins can be mentioned.

  Usually, these resin fine particles are obtained by an emulsion polymerization method. The surfactants, polymerization initiators, etc. used there may be those used in conventional methods. Regarding the method for synthesizing the resin fine particles, for example, U.S. Pat. Nos. 2,852,368, 2,853,457, 3,411,911, 3,411,912, 4,197,127. Belgian Patent Nos. 688,882, 691,360, 712,823, JP-B 45-5331, JP-A-60-18540, 51-130217, 58-137831, 55-50240 and the like.

  The resin fine particles used in the present invention preferably have an average particle size of 10 to 200 nm, more preferably 10 to 150 nm, and still more preferably 10 to 100 nm. If the average particle diameter of the resin fine particles is 10 nm or more, the resin fine particles do not penetrate into the void layer of the void type recording medium and are present on the surface of the void layer, which is preferable in terms of gloss. If the average particle size of the resin fine particles is 200 nm or less, the resin fine particles are small to some extent, which is advantageous from the viewpoint of leveling properties on the surface of the void layer, and is preferable in terms of gloss. The average particle size of the resin fine particles can be easily obtained using a commercially available particle size measuring device using a light scattering method or a laser Doppler method, for example, Zetasizer 1000 (manufactured by Malvern).

  In the ink of the present invention, the content of the resin fine particles in the recording ink is preferably 0.2 to 10% by mass, and more preferably 0.5 to 5% by mass. If the addition amount of the resin fine particles is 0.2% by mass or more, a sufficient effect on the color fading property can be exhibited. If the addition amount is 10% by mass or less, the ink ejection property becomes more stable, and further during storage. This is more preferable because it can suppress an increase in ink viscosity.

  In the resin fine particles according to the present invention, the minimum film-forming temperature (MFT) is preferably −60 to 60 ° C. In the present invention, a film-forming aid may be added to control the minimum film-forming temperature of the resin fine particles. The film-forming aid, also called a plasticizer, is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the resin latex. For example, “Synthetic Latex Chemistry (written by Soichi Muroi, published by Kobunshi Shuppankai (1970)” )"It is described in.

  The ink of the present invention can contain an organic solvent. The organic solvent is not particularly limited, but a water-soluble organic solvent is preferable, and specific examples include alcohols, polyhydric alcohols, polyhydric alcohol ethers, amines, amides, and heterocyclic rings. Specific examples of the compound include water-soluble organic solvents exemplified in JP-A No. 2003-231832.

  Various surfactants can be used in the ink of the present invention. The surfactant that can be used in the present invention is not particularly limited, but examples thereof include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxy Nonionic surfactants such as ethylene alkylallyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. In particular, an anionic surfactant and a nonionic surfactant can be preferably used.

  In the ink of the present invention, in addition to the above description, if necessary, the output stability, print head and ink cartridge compatibility, storage stability, image storage stability, and other various performance improvement objectives are known. Various additives such as a viscosity modifier, a specific resistance modifier, a film forming agent, an ultraviolet absorber, an antioxidant, a fading inhibitor, an antifungal agent, a rust inhibitor, etc. can be appropriately selected and used. Oil droplets such as liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicon oil, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57 -74192, 57-87989, 60-72785, 61-146591, JP-A-1-95091 and 3-13376, etc. Anti-fading agents, fluorescent whitening agents described in JP-A-59-42993, JP-A-59-52689, JP-A-62-2280069, JP-A-61-228771, JP-A-4-219266, and the like. be able to.

  The ink of the present invention preferably has a surface tension of 40 mN / m or less, more preferably 20 to 40 mN / m, in order to stably discharge, to increase the appearance of high gloss and to improve ozone resistance. . For the same reason, the ink viscosity is preferably 1.5 to 10 mPa · s, more preferably 3.0 to 8 mPa · s.

(recoding media)
Next, an ink jet recording medium (hereinafter also simply referred to as a recording medium) preferable for recording using the ink of the present invention will be described.

  As the recording medium that can be used in the ink jet recording method of the present invention, various papers such as plain paper, coated paper, and exclusive glossy paper can be used, but preferred recording media are water-resistant supports such as resin-coated paper and films. A void-type recording medium provided with a void-type ink absorbing layer mainly composed of a filler and a binder on the body, and particularly a high-gloss recording medium, is preferable because the effect of the present invention is further exhibited.

  The 60 ° gloss of the recording medium of the present invention is preferably 40% or more. This is because, when the 60 ° gloss is high, not only the glossiness of appearance is excellent but also the ozone gas resistance is surprisingly excellent. In particular, the ozone gas resistance is excellent in a portion where the ink amount is small. In addition, the occurrence of fading unevenness due to ozone gas is less advantageous and is further advantageous. In order to enhance the above effect, the 60 ° gloss is preferably 50% or more, more preferably 60% or more.

  Although there are still many unclear points regarding the relationship between gloss, ozone gas resistance, and discoloration unevenness of the recording medium, it affects the diffusion of the resin component in the ink due to the surface condition of the recording medium reflected in the gloss of the recording medium, and film formability It is estimated that The 60 ° gloss of the recording medium can be adjusted by selecting the recording medium, particularly the surface layer filler, the binder, and the filler / binder ratio.

(Inkjet recording method)
The printer used in the ink jet recording method of the present invention has a recording medium storage unit, a transport unit, an ink cartridge, and an ink jet print head, like a commercially available printer. Further, if necessary, a printer provided with a roll-shaped recording medium storage unit, a cutting unit, a print sorting device, and a print storage unit is useful for commercial use of inkjet photographs.

  The recording head may be any of a piezo method, a thermal method, and a continuous method, but the piezo method is preferable from the viewpoint of stability in ink ejection.

  In the inkjet recording method of the present invention, for the purpose of accelerating the film formation of the polymer fine particles contained in the recording ink, the recording medium is heated before recording or at the time of recording, or the print is heated or pressurized after recording. One step can be applied.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
(Preparation of inks 1 to 15)
Inks 1 to 15 were prepared with the following compositions. Inks 1 to 15 were prepared as a set of dark ink and light ink, respectively.

Diethylene glycol 10%
Glycerin 10%
Triethylene glycol monobutyl ether 10%
Surfinol 465 (manufactured by Air Products) 0.5%
Dye (see Table 1 for types)
The total amount of pure water is 100%. Note that the amount of dye added was such that the light absorbency at the maximum visible absorption wavelength of ink was 300 for light-colored inks, and that the light absorbency was 900 for dark-colored inks. Absorbance was determined by diluting the ink with pure water and multiplying the dilution ratio at that time by the absorbance after dilution.

  Comparative dye 1 is shown below.

(Preparation of inks 16 to 30)
Polyethylene glycol (number average molecular weight = 6000), which is one type of water-soluble resin, was added to inks 1 to 15 at a solid content of 1.6% to prepare inks 16 to 30, respectively.

(Preparation of inks 31 to 45)
Super Ink 300 (urethane latex, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a kind of resin fine particles, was added to inks 1 to 15 at a solid content of 1% to prepare inks 31 to 45, respectively.

[Production of recording medium]
(Recording medium 1)
The following components were coated on a resin-coated base paper having a thickness of about 220 μm so as to have the following amounts to produce a recording medium 1. An appropriate amount of activator and boric acid were added and used.

A-300 (gas phase method silica, primary average particle size 7 nm, manufactured by Nippon Aerosil Industry Co., Ltd.)
22.0 g / m ²
PVA235 (polyvinyl alcohol, manufactured by Kuraray Co.) 3.9 g / m ²
Cationic polymer P-1 2.3 g / m ²

(Recording medium 2)
On the recording medium 1, a surface layer comprising the following components was applied.

A300 1.0 g / m ²
PVA235 0.2 g / m ²
Cationic polymer P-1 0.1 g / m ²
(Recording medium 3)
On the recording medium 1, a surface layer comprising the following components was applied.

A300 1.0 g / m ²
PVA235 0.25 g / m ²
Cationic polymer P-1 0.1 g / m ²
(Recording medium 4)
On the recording medium 1, a surface layer comprising the following components was applied.

A300 1.0 g / m ²
PVA235 0.33 g / m ²
Cationic polymer P-1 0.1 g / m ²
(Recording medium 5)
On the recording medium 1, a surface layer comprising the following components was applied.

Colloidal silica (average particle size 0.6 μm) 1.2 g / m ²
PVA235 0.25 g / m ²
Cationic polymer P-1 0.06 g / m ²
Table 1 shows the 60 ° gloss of the produced recording medium.

[Evaluation of ink]
The prepared ink set (dark color, light color) was filled as dark magenta and light magenta of an ink cartridge of PM-740DU (manufactured by Seiko Epson), and an image was formed on the recording medium to produce a 10-color wedge of pure color. . The obtained recording prints were naturally dried for 24 hours, and then evaluated as follows.

(Light resistance)
The magenta wedge was irradiated with a xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.) at an illuminance of 70000 lx for 240 hours. The reflection density before and after the irradiation of the 3, 5, and 7 steps of the wedge was measured, the residual density ratio was measured, and the average value was obtained.

(Acid gas resistance)
It was exposed for 30 hours at an ozone concentration of 10 ppm with an ozone gas tester (Suga Test Instruments Co., Ltd., ozone weather meter OMS-H). The reflection density before and after exposure of the 3, 5, and 7 steps of the wedge was measured, the residual density ratio was measured, and the average value was obtained.

(Ozone fading unevenness)
Evaluation by the ozone gas tester The ozone fading unevenness in the wedge was evaluated according to the following criteria.

6: No discoloration unevenness is observed in all stages. 5: Very slight unevenness at 3 steps or less, but not noticeable. 4: Unevenness is observed at 3 steps or less, but the density is low and not so noticeable. Slightly uneven, but inconspicuous 2: Unevenness is observed even at 4-5 stages. Unevenness is observed even at 1: 7-6 stages.

  As is apparent from Table 1, it can be seen that the ink of the present invention is superior in light resistance, acid gas resistance, and ozone fading unevenness as compared with the comparative ink.

Claims (4)

An ink-jet ink comprising at least one dye represented by the following general formulas (1) to (14) and a resin component.

(Wherein R ₁₁ represents a branched alkyl group, a cycloalkyl group, a heterocyclic group or an amino group, R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom or a substituent, and n11 represents an integer of 1 to 3. N12 represents an integer of 1 to 4.)

(In the formula, R ₂₁ represents a heterocyclic group, R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom or a substituent, n ₂₁ represents an integer of 1 to 3, and n ₂₂ represents an integer of 1 to 4. )

(Wherein R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ each represent a hydrogen atom or a substituent, and n ₃₁ represents an integer of 1 to 3)

Wherein R ₄₁ , R ₄₂ and R ₄₃ each represent a hydrogen atom or a substituent, n41 represents an integer of 1 to 3, and Z forms a 5- to 7-membered heterocyclic group together with the carbon atom. Represents a group of non-metallic atoms necessary for

(In the formula, R ₅₁ , R ₅₂ , and R ₅₃ each represent a hydrogen atom or a substituent, n51 represents an integer of 1 to 3, and n52 represents an integer of 1 to 4.)

(In the formula, R ₆₁ , R ₆₂ , R ₆₃ , and R ₆₄ each represent a hydrogen atom or a substituent, and n ₆₁ represents an integer of 1 to 3)

(Wherein R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ each represents a hydrogen atom or a substituent, and n71 represents an integer of 1 to 3)

(In the formula, R ₈₁ , R ₈₂ and R ₈₃ each independently represents a hydrogen atom or a substituent, n81 represents an integer of 1 to 3, and n82 represents an integer of 1 or 2.)

(In the formula, R ₉₁ , R ₉₂ , R ₉₃ and R ₉₄ each independently represents a hydrogen atom or a substituent, n91 represents an integer of 1 to 3, and n92 represents an integer of 1 or 2.)

(Wherein R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R ₁₀₄ each independently represents a hydrogen atom or a substituent, and n ₁₀₁ represents an integer of 1 to 3)

(In the formula, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ each independently represents a hydrogen atom or a substituent, and n ₁₁₁ represents an integer of 1 to 3.)

(Wherein R ₁₂₁ , R ₁₂₂ , R ₁₂₃ , R ₁₂₄ and R ₁₂₅ each independently represent a hydrogen atom or a substituent, and n121 represents an integer of 1 to 3)

(In the formula, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ , and R ₁₃₄ each independently represent a hydrogen atom or a substituent, n131 represents an integer of 1 to 3, and n132 represents an integer of 1 or 2.)

(In the formula, R ₁₄₁ , R ₁₄₂ , R ₁₄₃ and R ₁₄₄ each independently represent a hydrogen atom or a substituent, n141 represents an integer of 1 to 3, and n142 represents an integer of 1 to 4). The inkjet ink according to claim 1, wherein the resin component is resin fine particles. 3. An ink jet recording method comprising: recording on a void type ink jet recording medium using the ink jet ink according to claim 1. The inkjet recording method according to claim 3, wherein the 60 ° specular gloss of the void-type inkjet recording medium is 40% or more.