JP4972317B2 - Ink composition, ink set, recording method and recorded matter thereby - Google Patents

Description

  The present invention relates to an ink composition, an ink set, a recording method, and a recorded matter thereby, and in particular, an ink composition, an ink set, and a recording method for improving gas resistance, light resistance, bleeding, and bronzing of a recorded image, And the recorded material.

  The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording. Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force. As the ink for ink jet, water-based ink, oil-based ink, or solid (melted type) ink is used.

  For dyes used in such inkjet inks, good solubility in solvents such as water, high-density recording is possible, hue is good, light, heat, in the environment It is robust against active gases (SOx, etc. in addition to oxidizing gases such as NOx and ozone), has excellent fastness to water and chemicals, has good fixability to image receiving materials, and is difficult to bleed, ink It is required to have excellent storage stability, no toxicity, high purity, and availability at low cost.

  In particular, it is a dye that is fast to light, humidity, and heat, and in particular, when printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles, it is oxidative such as ozone in the environment. It is strongly desired to be robust against gas and excellent in water resistance. On the other hand, an image printed on plain paper has a problem that the superiority with respect to fastness is reduced.

  Known methods for improving the fastness of plain paper include (Patent Document 1 to Patent Document 4). However, depending on the printing conditions, the fastness is not sufficiently improved. The concentration is also insufficient.

  As described above, various effects can be obtained by using the additive, but it is difficult to use the conventional additive alone while maintaining various performances, and the robustness of the porous paper and the fastness of the plain paper are difficult to use. It is difficult to achieve both, and therefore, development of a coloring material based on a new idea that has not been achieved in the past and securing of fastness and a fundamental improvement in printing density by additives have been desired.

JP 2000-154342 A JP2002-3768 JP-A-2004-27037 JP 2004-169045 A

The objects of the present invention are as follows: (1) Absorption characteristics excellent in color reproducibility as yellow of the three primary colors, sufficient fastness against active gas in light, heat, humidity and environment, and bronze Providing a novel ink composition in which the phenomenon does not occur,
(2) In particular, it has a good hue due to the use of yellow azo dyes, has high fastness to active gases in the light and the environment, especially ozone gas, has excellent water resistance, and is fast even when printed on plain paper. Providing an ink composition for ink jet recording and an ink jet recording method capable of forming an image having excellent properties,
It is in.

式中、Ｇはヘテロ環基を表し、ｎは２又は３を表す。ｎが２の時は、Ｒ、Ｘ、Ｙ、Ｚ、Ｑ、Ｇは一価または２価の置換基を表し、少なくとも１つは２価の置換基を表す。ｎが３の時は、Ｒ、Ｘ、Ｙ、Ｚ、Ｑ、Ｇは一価、２価または３価の置換基を表し、少なくとも二つが２価の置換基を表すかまたは少なくとも１つが３価の置換基を表す。
一般式（Ｉ）

式中、Ｒ_１は炭素数５〜４０のアルキル基を表し、ｍ^１、ｎ^１、ｏ^１はそれぞれエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドの平均付加モル数を表し、０〜４０の数である。但し、ｍ^１、ｎ^１、ｏ^１の全てが０のことはない。
一般式（ＩＩ）

式中、Ｒ_２は炭素数５〜４０のアルキル基を表し、ｍ^２、ｎ^２、ｏ^２はそれぞれエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドの平均付加モル数を表し、０〜４０の数である。但し、ｍ^２、ｎ^２、ｏ^２の全てが０のことはない。
一般式（ＩＩＩ）

式中、Ｒ_３、Ｒ_４はそれぞれ独立に、炭素数１〜１８のアルキル基を表わす。Ｒ_５は水素原子、炭素数１〜６のアルキル基、またはフェニルを表す。ｍ^３、ｎ^３、ｏ^３はそれぞれエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドの平均付加モル数を表し、０〜４０の数である。但し、ｍ^３、ｎ^３、ｏ^３の全てが０のことはない。Ｘは、水素原子、または

を表す。ここで、Ｒ_６、Ｒ_７はそれぞれ独立に、炭素数１〜１８のアルキル基を表す。Ｒ８は水素原子、炭素数１〜６のアルキル基、またはフェニルを表す。ｍ^４は、エチレンオキサイドの平均付加モル数を表し、ｍ^３＋ｍ^４は０〜１００の数である。但し、ｍ^３＝０の時Ｒ_５は水素原子を表し、ｍ^４＝０の時Ｒ_８は水素原子を表す。また、Ｘが水素原子のときは、ｍ^３は１〜１００の数である。
〔２〕
式（Ｉ）〜（ＩＩＩ）で表される化合物を０．００１〜１５重量％含有することを特徴とする〔１〕に記載のインク組成物。
〔３〕
〔１〕または〔２〕に記載のインク組成物を含むことを特徴とするインクセット。
〔４〕
〔１〕〜〔３〕のいずれか一項に記載のインク組成物を記録媒体上に付与することを特徴とする記録方法。
〔５〕
〔１〕〜〔３〕のいずれか一項に記載のインク組成物の液滴を記録媒体上に吐出させて記録を行うことを特徴とする記録方法。
〔６〕
〔４〕または〔５〕に記載の記録方法を用いて記録されたことを特徴とする記録物。
本発明は上記〔１〕〜〔６〕にかかるものであるが、その他の事項についても参考のため記載した。
（１）
下記一般式（Ｙ−Ｉ）で表される化合物及びその塩からなる群から選ばれる少なくとも一種の化合物と、下記一般式（Ｉ）から（ＩＩＩ）で表される化合物から選ばれる少なくとも１種を含有することを特徴とするインク組成物。 [1]
At least one compound selected from the group consisting of compounds represented by the following general formula (Y-I) and salts thereof, and at least one selected from compounds represented by the following general formulas (I) to (III): An ink composition comprising the ink composition.
When G further has a substituent, the substituent is a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched aralkyl group having 7 to 18 carbon atoms, a linear chain having 2 to 12 carbon atoms, or Branched alkenyl group, linear or branched alkynyl group having 2 to 12 carbon atoms, linear or branched cycloalkyl group having 3 to 12 carbon atoms, linear or branched cycloalkenyl group having 3 to 12 carbon atoms, halogen Atom, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group, aryloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino Group, alkylthio group, arylthio group, alkyloxycarbonylamino group, alkylsulfonylamino group and arylsulfonylamino group, carbamoyl Group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group , An aryloxycarbonyl group, an acyl group and an ionic hydrophilic group.
When R, X, Y, Z and Q are monovalent substituents, each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic ring Group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group) Arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio Group, ants Ruthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphini It represents a ruoxy group, a phosphinylamino group, a silyl group, an azo group, or an imide group, and these may further have the substituent mentioned in the G.
When R, X, Y, Z and Q are divalent substituents, each independently an alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, -O-, -CO-, —NR′— (R ′ represents a hydrogen atom, an alkyl group or an aryl group), —S—, —SO ₂ —, —SO—, —NHCH ₂ CH ₂ NH—, or —NHCONH—, Further, it may have the substituent mentioned in the G.
When R, X, Y, Z and Q are trivalent substituents, each independently represents a trivalent hydrocarbon group, a trivalent heterocyclic group,>N-,> NCH ₂ CH ₂ NH— or> Represents NCONH-.
Formula (Y-I):

In the formula, G represents a heterocyclic group, and n represents 2 or 3. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of
Formula (I)

In the formula, R ₁ represents an alkyl group having 5 to 40 carbon atoms, and m ¹ , n ¹ , and o ¹ represent average addition mole numbers of ethylene oxide, propylene oxide, and butylene oxide, and are 0 to 40. . However, all of m ¹ , n ¹ , and o ¹ are not 0.
Formula (II)

In the formula, R ₂ represents an alkyl group having 5 to 40 carbon atoms, and m ² , n ² , and o ² represent average added mole numbers of ethylene oxide, propylene oxide, and butylene oxide, and are 0 to 40. . However, all of m ² , n ² , and o ² are not 0.
Formula (III)

In the formula, R ₃ and R ₄ each independently represents an alkyl group having 1 to 18 carbon atoms. R ₅ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or phenyl. m ³ , n ³ , and o ³ represent the average number of moles added of ethylene oxide, propylene oxide, and butylene oxide, respectively, and are numbers from 0 to 40. However, all of m ³ , n ³ , and o ³ are not 0. X is a hydrogen atom, or

Represents. Here, R < ₆ >, R < ₇ > represents a C1-C18 alkyl group each independently. R8 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or phenyl. m ⁴ represents the average number of moles added of ethylene oxide, and m ³ + m ⁴ is a number from 0 to 100. However, when m ³ = 0, R ₅ represents a hydrogen atom, and when m ⁴ = 0, R ₈ represents a hydrogen atom. Further, when X is a hydrogen atom, ^{m 3} is a number from 1 to 100.
[2]
The ink composition as described in [1], which contains 0.001 to 15% by weight of a compound represented by formulas (I) to (III).
[3]
An ink set comprising the ink composition according to [1] or [2].
[4]
A recording method comprising applying the ink composition according to any one of [1] to [3] onto a recording medium.
[5]
[1] to [3] A recording method, wherein recording is performed by discharging droplets of the ink composition according to any one of [1] to [3] onto a recording medium.
[6]
A recorded matter recorded using the recording method according to [4] or [5].
The present invention relates to the above [1] to [6], but other matters are also described for reference.
(1)
At least one compound selected from the group consisting of compounds represented by the following general formula (Y-I) and salts thereof, and at least one selected from compounds represented by the following general formulas (I) to (III): An ink composition comprising the ink composition.

Formula (Y-I):

  In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of

Formula (I):

In the formula, R ₁ represents an alkyl group having 5 to 40 carbon atoms, and m ¹ , n ¹ , and o ¹ represent average addition mole numbers of ethylene oxide, propylene oxide, and butylene oxide, and are 0 to 40. . However, all of m ¹ , n ¹ , and o ¹ are not 0.

General formula (II):

In the formula, R ₂ represents an alkyl group having 5 to 40 carbon atoms, and m ² , n ² , and o ² represent average added mole numbers of ethylene oxide, propylene oxide, and butylene oxide, and are 0 to 40. . However, all of m ² , n ² , and o ² are not 0.

Formula (III)

In the formula, R ₃ and R ₄ each independently represents an alkyl group having 1 to 18 carbon atoms. R ₅ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or phenyl. m ³ , n ³ , and o ³ represent the average number of added moles of ethylene oxide, propylene oxide, and butylene oxide, and are numbers from 0 to 40. However, all of m ³ , n ³ , and o ³ are not 0. X is a hydrogen atom, or

Represents. Here, R < ₆ >, R < ₇ > represents a C1-C18 alkyl group each independently. R ₈ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or phenyl. m ⁴ represents the average number of moles added of ethylene oxide, and m ³ + m ⁴ is a number from 0 to 100. However, when m ³ = 0, R ₅ represents a hydrogen atom, and when m ⁴ = 0, R ₈ represents a hydrogen atom. Further, when X is a hydrogen atom, ^{m 3} is a number from 1 to 100.
(2) The ink composition as described in (1), which contains 0.001 to 15% by weight of a compound represented by formulas (I) to (III).
(3) An ink set comprising the ink composition according to (1) or (2).
(4) A recording method comprising applying the ink composition according to any one of (1) to (3) onto a recording medium.
(5) A recording method, wherein recording is performed by discharging droplets of the ink composition according to any one of (1) to (4) onto a recording medium.
(6) A recorded matter recorded using the recording method according to (4) or (5).

  According to the present invention, an ink composition that is excellent in color reproducibility, has sufficient fastness to light, heat, humidity, and an active gas in the environment, and can form a yellow image that does not cause bronzing (preferably Ink composition for ink jet recording) is provided, and further, an ink jet recorded product and an ink jet recording method of an image having excellent weather resistance of plain paper are provided.

Hereinafter, the present invention will be described in detail.

Hereinafter, the yellow dye useful in the present invention will be described in detail.
The ink composition of the present invention contains a compound represented by the following general formula (Y-I).

Formula (Y-I):

In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of
The compound represented by the general formula (Y-I) functions as a yellow dye. The ink composition of the present invention is preferably a yellow ink composition.

Hereinafter, the general formula (Y-I) will be described in detail.
In the general formula (Y-I), preferable examples of the substituent of G are preferably a 5- to 8-membered heterocyclic group, and among them, a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group. Are preferred, and they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

  Examples of the heterocyclic group represented by G include pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan. , Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazo Examples include lysine, thiazoline, sulfolane and the like.

  When the heterocyclic group is a group that can further have a substituent, the heterocyclic group may further have the following substituents.

  C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (the above groups having a branched chain are dissolved in a dye) Preferred are those having an asymmetric carbon, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonyl. Ethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (eg, chlorine atom, bromine atom), aryl group (eg, phenyl, 4-t- Butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, Nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy) , 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino groups (for example, acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), alkylamino Group (for example, Methylamino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg, phenylamino, 2-chloroanilino), ureido groups (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino A group (for example, N, N-dipropylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), alkylsulfonylamino groups and arylsulfonylamino groups (eg methylsulfonylamino, phenylsulfonylamino, p Toluenesulfonylamino), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl) ), A sulfonyl group (for example, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), an alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazole-5) -Oxy, 2-tetrahydropyranyloxy), azo groups (eg phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy groups (example For example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino) , An imide group (for example, N-succinimide, N-phthalimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2 -Pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), Sill group (e.g., acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (e.g., carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

  In the general formula (I), examples of preferable substituents of Q, R, X, Y and Z will be described in detail.

  When Q, R, X, Y and Z represent a monovalent group, the monovalent group represents a hydrogen atom or a monovalent substituent. The monovalent substituent will be described in more detail. Examples of the monovalent substituent include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an alkoxy group, and an aryl group. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonyl Amino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, A silyl group, an azo group, or an imide group can be mentioned, and each may further have a substituent.

  Among them, particularly preferred are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group. An arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group, and a hydrogen atom, an alkyl group Most preferred are groups, aryl groups, cyano groups, or alkylsulfonyl groups.

  Hereinafter, Q, R, X, Y, and Z will be described in more detail.

  The halogen atom represented by Q, R, X, Y and Z represents a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

  The alkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Of these, a hydroxy group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in a salt form) or a carboxyl group (may be in a salt form) is preferable. Examples of the alkyl group include methyl, ethyl, butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfobutyl.

  The cycloalkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

  The aralkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted aralkyl group. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aralkyl include benzyl and 2-phenethyl.

  The alkenyl group represented by Q, R, X, Y and Z represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Preferred examples include C2-C30 substituted or unsubstituted alkenyl groups such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like.

  The alkynyl group represented by Q, R, X, Y and Z is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

  The aryl group represented by Q, R, X, Y and Z is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoyl. Aminophenyl. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent.

  The heterocyclic group represented by Q, R, X, Y and Z is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. A group, which may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic group include, but are not limited to, the substitution position. Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Can be mentioned.

  The alkoxy group represented by Q, R, X, Y and Z includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

  The aryloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

  The silyloxy group represented by Q, R, X, Y and Z is preferably a silyloxy group having 3 to 20 carbon atoms, and examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

  The heterocyclic oxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

  The acyloxy group represented by Q, R, X, Y and Z is a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms. An oxy group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group which can further have a substituent. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups.
Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl. Examples include oxy.

  The alkoxycarbonyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further substituted. Examples thereof include the same substituents as mentioned when the group can be included. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

  The aryloxycarbonyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples thereof include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

  The amino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of the group include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino And so on.

  The acylamino group represented by Q, R, X, Y and Z is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms. An amino group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

  The aminocarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

  The alkoxycarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further substituted. Examples thereof include the same substituents as mentioned when the group can be included. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

  The aryloxycarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

  The sulfamoylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

  The alkyl and arylsulfonylamino groups represented by Q, R, X, Y and Z are substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms. An amino group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the alkylsulfonylamino group and arylsulfonylamino group include, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like. I can do it.

  The alkylthio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

  The arylthio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. As an example of the substituent, the G may further have a substituent. And the same substituents as mentioned when they are small groups. Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

  The heterocyclic thio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

  The sulfamoyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the sulfamoyl group include, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl. N- (N′-phenylcarbamoyl) sulfamoyl) and the like.

  The alkyl and arylsulfinyl groups represented by Q, R, X, Y and Z are preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkyl and arylsulfinyl groups include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

  The alkyl and arylsulfonyl groups represented by Q, R, X, Y and Z are preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

  The acyl group represented by Q, R, X, Y and Z is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferable, and examples of the substituent include a group in which G can further have a substituent. Examples are the same as the substituents sometimes mentioned. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

  The aryloxycarbonyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

  The alkoxycarbonyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

  The carbamoyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

  The phosphino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

  The phosphinyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

  The phosphinyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

  The phosphinylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

  The silyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

  Examples of the azo group represented by Q, R, X, Y, and Z include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. I can do it.

  Examples of the imide group represented by Q, R, X, Y, and Z include N-succinimide and N-phthalimide.

When Q, R, X, Y and Z represent a divalent group, examples of the divalent group include an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene) and an alkenylene group (eg, ethenylene, propylene). Nylene), alkynylene groups (eg, ethynylene, propynylene), arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl groups) , Pyrimidine-2,4-diyl group, pyrimidine-4,6-diyl group, quinoxaline-2, 3-diyl group, pyridazine-3,6-diyl), -O-, -CO-, -NR '-( R 'is a hydrogen atom, an alkyl group or an aryl _{group), - S -, - SO} 2 -, - SO- , or a combination thereof (e.g., -NHCH ₂ CH ₂ NH -, - it is good is NHCONH-, etc.) Arbitrariness.

  The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent.

  Examples of the substituent are the same as the substituent described in G above.

  The alkyl group and aryl group for R ′ have the same meanings as the examples of the substituent for G.

More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, a divalent heterocyclic group, -S-,- More preferably, it is SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.).

  The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

When Q, R, X, Y and Z represent a trivalent group, the trivalent group includes a trivalent hydrocarbon group, a trivalent heterocyclic group,> N-, or a divalent group thereof. (For example,> NCH ₂ CH ₂ NH—,> NCONH—, etc.).

  The total carbon number of the trivalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  In general formula (I), preferred examples of n are 1 or 2, with 2 being particularly preferred.

  In general formula (I), a preferred example of a substituent for X is an electron-withdrawing group. In particular, it is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and more preferably an electron-withdrawing group having a σp value of 0.30 or more. The upper limit is 1.0 or less electron withdrawing group.

  Specific examples of X which is an electron-withdrawing group having a σp value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphosphono group Diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, A halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, a heterocyclic group, a halogen atom, Azo group or selenocyane Group.

  Preferred examples of X include an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, and 7 to 18 carbon atoms. Aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, 6 to 6 carbon atoms 18 arylsulfonyl groups, C 0-12 sulfamoyl groups, C 1-12 halogenated alkyl groups, C 1-12 halogenated alkyloxy groups, C 1-12 halogenated alkylthio groups, carbon A halogenated aryloxy group having 7 to 18 carbon atoms, an aryl group having 7 to 18 carbon atoms substituted with two or more other electron-withdrawing groups having a σp of 0.20 or more, Fine nitrogen atom, an oxygen atom or 5-8 membered ring having sulfur atom include a heterocyclic group having 1 to 18 carbon atoms.

  More preferably, they are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms.

  Particularly preferable as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and the most preferable one is a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms. It is.

  In the general formula (I), preferred examples of the substituent for Z are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group. Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

  Detailed examples of the substituent represented by Z are the same as the corresponding examples of the substituent described in the example of the heterocyclic group represented by G, and preferred examples are also the same.

  A particularly preferred substituent represented by Z is a substituted aryl group or a substituted heterocyclic group, and among these, a substituted aryl group is particularly preferred.

  In formula (I), preferred examples of the substituent for Q are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted aryl. A sulfonyl group is preferable, and a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group is preferable, and a hydrogen atom is particularly preferable among them.

  In general formula (I), R represents a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C4. A C12 heterocyclic group is preferred, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, a secondary or tertiary alkyl group is particularly preferred, and a t-butyl group is most preferred.

  In general formula (I), Y represents a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon. A heterocyclic group having a number of C4 to C12 is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1 to C8 and / or a branched alkyl group is preferable, and a hydrogen atom or a C1 to C8 alkyl group is particularly preferable. Preferably, a hydrogen atom is most preferable.

  Regarding the preferred combination of substituents of the dye represented by the general formula (I) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the coloring matter represented by the general formula (I) of the present invention includes the following (A) to (G).

(I) G is preferably a 5- to 8-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring. -A triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

(B) R represents a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted heterocyclic group having a total carbon number of C4 to C12. Among them, a straight chain alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, a secondary or tertiary alkyl group is particularly preferable, and a t-butyl group is most preferable.

(C) Particularly preferred as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, a cyano group Or an alkylsulfonyl group having 1 to 12 carbon atoms, and a most preferred one is a cyano group.

(D) Y is a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C12. Among these, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms in total or a branched alkyl group is preferable, and a hydrogen atom or a C1 to C8 alkyl group is particularly preferable. Most preferred.

(E) Z is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a particularly preferred substituent is a substituted aryl group or a substituted heterocyclic group, and among them, a substituted aryl group is particularly preferred.

(F) Q is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, particularly a hydrogen atom, A substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group is preferable, and a hydrogen atom is particularly preferable among them.

(G) n represents an integer of 1 to 3, preferably 1 or 2, and most preferably 2.

  The compound represented by the general formula (Y-I) is represented by the following general formula (Y-1), general formula (Y-2), general formula (Y-3), general formula (Y-4) or general formula ( A compound represented by any one of Y-5) is preferred.

General formula (Y-1):

In the formula, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle M represents a hydrogen atom or a cation. m ₁ represents an integer of 0 to 3.

General formula (Y-2):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₁ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₂₁ and m ₂₂ each independently represent an integer of 0 to 3.

General formula (Y-3):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group, L ₂ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.

General formula (Y-4):

In the formula, R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₃ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.

General formula (Y-5):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₄ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.

The compound represented by the general formula (Y-I) is represented by the following general formula (Y-1), general formula (Y-2), general formula (Y-3), general formula (Y-4) or general formula ( In Y-5), the nitrogen-containing heterocycle composed of G, G ₁ and G ₂ is preferably an S-triazine ring.
Specific examples ( DYE- 1 to 26) of the dyes represented by formulas (Y-1) to (Y-5) are shown below, but the dyes used in the present invention are limited to the following examples. Is not to be done. The following DYE-1 to 6 do not correspond to the general formula (Y-I).

  Moreover, although the structure of the following specific examples is shown in the form of a free acid, it cannot be overemphasized that you may use in the form of arbitrary salts.

  Preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, or organic cations (eg, pyridinium, tetramethylammonium, guanidinium).

The ink composition of the present invention can be used in combination with a yellow dye other than the compounds represented by the general formulas (Y-1) to (Y-5).
Examples of the yellow dye used in combination include International Patent Publication WO2005 / 075573, Japanese Patent Application Laid-Open No. 2004-83903 (paragraph numbers [0024] to [0062]), and 2003-277661 (paragraph numbers [0021] to [0050]. ), 2003-277262 (paragraph numbers [0042] to [0047]), 2003-128953 (paragraph numbers [0025] to [0076]), 2003-41160 (paragraph numbers [0028] to [0064] ], U.S. Application Publication No. US2003 / 0213405 (paragraph number [0108]), and C.I. I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195 196, 197, 199, 218, 219, 222, 227, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40 and the following general formula (Y-6), general formula (Y-7) and the like can be mentioned, but are not limited thereto.

Formula (Y-6);

General formula (Y-7);

(In the general formulas (Y-6) and (Y-7), K ₁ , K ₂ , K ₁₁ , and K ₂₁ independently represent CH ₃ , OCH ₃ , and Z and Z ′ represent independently Represents a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group, which may be further condensed, and Z and Z ′ are the same as each other. Or different.

The yellow dye used in the present invention is preferably a dye having an oxidation potential nobler than 1.0 V (vs SCE) and more nobler than 1.1 V (vs SCE) in terms of fastness and fastness to ozone gas. Certain dyes are more preferred, and dyes that are noble above 1.2 V (vs SCE) are particularly preferred.
A person skilled in the art can easily measure the value of the oxidation potential (Eox). Regarding this method, for example Delahay's “New Instrumental Methods in Electrochemistry” (published by Interscience Publishers, 1954) J. et al. "Electrochemical Methods" by Bard et al. (Published by John Wiley & Sons in 1980) and "Electrochemical Measurement Method" by Akira Fujishima et al. (Published by Gihodo Publishing Co., Ltd. in 1984).

Specifically, the oxidation potential is determined by placing a test sample in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate at 1 × 10 ⁻² to 1 × 10 ⁻⁶ mol / L (liter) is dissolved and measured as a value for SCE (saturated calomel electrode) using various voltammetry (polarography using a dropping mercury electrode, cyclic voltammetry, method using a rotating disk electrode). Although this value may be deviated by several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, the reproducibility of the potential can be ensured by inserting a standard sample (for example, hydroquinone).
In order to uniquely define the potential, in the present invention, in N, N-dimethylformamide containing 0.1 moldm ^-3 tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the dye is 10 ^-3 mol / L). The value (vs SCE) measured using SCE (saturated calomel electrode) as a reference electrode, a graphite electrode as a working electrode, and a platinum electrode as a counter electrode is taken as the oxidation potential of the dye.

  The value of Eox represents the ease of electron transfer from the sample to the electrode, and the larger the value (the oxidation potential is noble), the more difficult the electron transfer from the sample to the electrode, in other words, the less easily oxidized. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing an electron withdrawing group, and the oxidation potential becomes lower by introducing an electron donating group. In the present invention, in order to lower the reactivity with ozone, which is an electrophile, it is desirable to introduce an electron withdrawing group into the yellow dye skeleton to make the oxidation potential more noble.

  In addition, the dye used in the present invention preferably has good fastness and good hue, and when used as a yellow color ink composition (yellow ink), the tail on the long wave side is cut off particularly in the absorption spectrum. It is preferable that it is good. Therefore, λmax is from 390 nm to 470 nm, and the ratio I (λmax + 70 nm) / I (λmax) between the absorbance I (λmax) of λmax and the absorbance I (λmax + 70 nm) of λmax + 70 nm is 0.20 or less. The yellow dye is preferably 0.15 or less, more preferably 0.10 or less. In addition, the absorption wavelength and absorbance defined here show values in a solvent (water or ethyl acetate).

Next, the surfactants represented by the general formulas (I) to (III) will be described. First, the surfactant represented by the general formula (I) will be described. In general formula (I), R ₁ represents an alkyl group having 5 to 40 carbon atoms, preferably 8 to 18 carbon atoms, which may be linear or branched and may be substituted. Examples of the group capable of substituting for the alkyl group represented by R ₁ include an aryl group (for example, phenyl, o-tolyl, p-tolyl, pt-butylphenyl), an alkoxy group (for example, methoxy, ethoxy, n-butoxy). Etc.), halogen atoms (for example, chlorine atom, bromine atom) and the like.

Specific examples of the alkyl group represented by R ₁ include n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, n-octadecyl, 2-ethylhexyl, 1-ethylpentyl. 1-n-butylpentyl, 1-n-pentylhexyl, 1-n-hexylheptyl, 1-n-heptyloctyl, 1-n-octylnonyl, 6-methoxyhexyl, 2-phenylethyl and the like. it can.

m ¹ represents the average number of moles of addition of ethylene oxide, n ¹ represents the average number of moles of addition of propylene oxide, o ¹ represents the average number of moles of addition of butylene oxide, and is a number from 0 to 40, preferably a number from 0 to 30. And particularly preferably a number of 0 to 20. However, all of m ¹ , n ¹ , and o ¹ are not 0.

Among the surfactants represented by the general formula (I) in the present invention, a nonionic surfactant represented by the following general formula (I-1) is particularly preferable.
Formula (I-1)

In General Formula (I-1), R ₁₁ and R ₁₂ are each a saturated hydrocarbon having 4 to 10 carbon atoms, the total number of carbon atoms of R ₁₁ and R ₁₂ is 8 to 18, and m ¹¹ is 3 It is a number of ~ 20. Examples of the saturated hydrocarbon having 4 to 10 carbon atoms represented by R ₁₁ and R ₁₂ include n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n -Nonyl, n-decyl, etc. can be mentioned. The total carbon number of R ₁₁ and R ₁₂ is 8 to 18, and 8 to 16 is more preferable. m ¹¹ is 3 to 20, more preferably from 5 to 20, more preferably from 6 to 18.

  Although the specific example of a compound represented by general formula (I-1) below is shown, it is not limited to these.

Next, the surfactant represented by the general formula (II) will be described. In the general formula (II), R ₂ represents an alkyl group having 5 to 40 carbon atoms, preferably 5 to 30 carbon atoms, which may be linear or branched, and may be substituted. Examples of the group capable of substituting for the alkyl group represented by R ₂ include an aryl group (eg, phenyl, o-tolyl, p-tolyl, pt-butylphenyl), an alkoxy group (eg, methoxy, ethoxy, n-butoxy). Etc.), halogen atoms (for example, chlorine atom, bromine atom) and the like. Specific examples of the alkyl group represented by R ₂ include n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, n-octadecyl, 2-ethylhexyl, 1-ethylpentyl. 1-n-butylheptyl, 1-n-hexylnonyl, 1-n-heptyldecyl, 1-n-octyldodecyl, 1-n-decyltetradecyl, 6-methoxyhexyl, 2-phenylethyl, etc. it can.

m ² is the average addition number of ethylene oxide, n ² is the average addition number of propylene oxide, o ² is the average addition number of butylene oxide, and is a number from 0 to 40, preferably a number from 0 to 30 Yes, particularly preferably a number from 0 to 20. However, all of m ¹ , n ¹ , and o ¹ are not 0.

Of the surfactants represented by the general formula (II) in the present invention, nonionic surfactants represented by the following general formula (II-1) are particularly preferred.
Formula (II-1)

In the general formula (II-1), R ₂₁ and R ₂₂ are each independently a saturated hydrocarbon group having 2 to 20 carbon atoms, preferably 4 to 13 carbon atoms. Examples of the saturated hydrocarbon group having 2 to 20 carbon atoms represented by R ₂₁ and R ₂₂ include ethyl, n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl. , N-nonyl, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl and the like. m ²¹ represents an average addition mole number of ethylene oxide, the number of 2 to 40, preferably the number of from 3 to 30.

  Specific examples of the surfactant represented by the general formula (II-1) are shown below, but are not limited thereto.

  Next, the surfactant represented by the general formula (III) will be described.

In general formula (III), R < ₃ >, R < ₄ > represents a C1-C18 alkyl group each independently. More specifically, R ₃ and R ₄ each independently represents an alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, n-propyl, butyl, hexyl, octyl, decyl, dodecyl, etc.) May be. Examples of the substituent include an alkyl group (for example, methyl, ethyl, isopropyl and the like), an alkoxy group (for example, methoxy, ethoxy and the like), a halogen atom (for example, a chlorine atom and a bromine atom) and the like. Of these, as R ₃ and R ₄ , an unsubstituted linear alkyl group having 1 to 12 carbon atoms or an unsubstituted branched alkyl group is preferable, and particularly preferable specific examples thereof include methyl, ethyl, n-butyl, 2- Examples include methylbutyl and 2,4-dimethylpentyl.

R ₅ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and the alkyl group and the phenyl group may be substituted. Examples of the substituent for the alkyl group represented by R ₅ include an alkyl group (for example, methyl, ethyl, isopropyl and the like), an alkoxy group (for example, methoxy, ethoxy and the like), and a phenyl group. Examples of the substituent for the phenyl group of R ₅ include an alkyl group (eg, methyl, ethyl, isopropyl, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), etc. Can be mentioned. R ₅ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom.

  X is a hydrogen atom, or

R ₆ and R ₇ each independently represents an alkyl group having 1 to 18 carbon atoms. Preferable substituents and specific examples of R ₆ and R ₇ include substituents and specific examples selected from the same group as R ₃ and R ₄ described above. R ₈ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and preferred specific examples thereof include substituents and specific examples selected from the same group as R ₅ described above. m ³ and m ⁴ each represent the average number of moles of ethylene oxide added, and m ³ + m ⁴ is 0 to 100, preferably 0 to 50, particularly preferably 0 to 40. Here, when m ³ = 0, R ₅ represents a hydrogen atom, and when m ⁴ = 0, R ₈ represents a hydrogen atom. Also when X represents a hydrogen atom, m ³ represents 1 to 100, preferably 1 to 50, particularly preferably represents 1 to 40.

  Specific examples of the nonionic surfactant represented by the general formula (III) are shown below, but are not limited thereto.

  The compound represented by the general formula (III) of the present invention can be easily obtained as a commercial product, and specific trade names thereof are Surfinol 61, 82, 104, 420, 440, 465, 485, 504. CT-111, CT-121, CT-131, CT-136, CT-141, CT-151, CT-171, CT-324, DF-37, DF-58, DF-75, DF-110D, DF -210, GA, OP-340, PSA-204, PSA-216, PSA-336, SE, SE-F, Dinol 604 (above, Nissin Chemical Co., Ltd. and Air Products), Orphine A, B, AK -02, CT-151W, E1004, E1010, P, SPC, STG, Y, 32W (the above, Nissin Chemical Co., Ltd.) and the like.

  The nonionic surfactants represented by the general formulas (I) to (III) of the present invention can be synthesized using a known method. For example, Takehiko Fujimoto's revised edition “New surfactants” It can be obtained by the method described in "Introduction" (1992), pages 94-107. In the present invention, the nonionic surfactants represented by the general formulas (I) to (III) may be used alone or in combination of two or more different nonionic surfactants. .

  The surfactant content including the nonionic surfactants represented by the general formulas (I) to (III) of the present invention is 0.001 to 15% by mass, preferably 0.005 to the ink composition. It is 10 mass%, More preferably, it is 0.01-5 mass%.

  The ink composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The ink of the present invention can be prepared by dissolving and / or dispersing the dye of the present invention in a lipophilic medium or an aqueous medium as a medium. Preferably, an aqueous medium is used.

  When the dye used in the present invention is dispersed in an aqueous medium, the dye and the oil-soluble polymer are used as described in JP-A-11-286637, JP-A-2001-240763, JP-A-2001-262039, JP-A-2001-247788. In a high-boiling organic solvent such as JP-A No. 2001-262018, JP-A No. 2001-240763, JP-A No. 2001-335734, JP-A No. 2002-80772, or the like. It is preferable to disperse the dye of the present invention in an aqueous medium. The specific method for dispersing the dye used in the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive and the amount used thereof are preferably those described in the above-mentioned patent documents. can do. Or you may disperse | distribute the said azo dye to a fine particle state with a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. Regarding the method for preparing the ink for ink jet recording, in addition to the above-mentioned patent documents, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, 7-118584, Details are described in JP-A-11-286637 and JP-A-2001-271003, and can also be used for preparing the ink for ink jet recording of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethylene , Tetramethylpropylenediamine) and other polar solvents (for example, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together. The water-miscible organic solvent is a material having functions such as an anti-drying agent, a penetration accelerator, and a wetting agent for inkjet recording ink.

  It is preferable to contain 0.1 to 20 parts by mass of the dye represented by the general formula (Y-I) used in the present invention in 100 parts by mass of the ink composition of the present invention. It is more preferable to contain 10 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 to 9 parts by mass. In the ink composition of the present invention, other dyes may be used in combination with the dye represented by formula (Y-I). When two or more kinds of dyes are used in combination, the total dye content is preferably within the above range.

  The ink composition obtained in the present invention includes a drying inhibitor (wetting agent) for preventing clogging due to dry operation at the ink jetting port, a penetration accelerator for allowing the ink to permeate the paper better, ultraviolet light Appropriate selection of additives such as absorbents, antioxidants, antifoaming agents, viscosity modifiers, surface tension modifiers, dispersants, dispersion stabilizers, antifungal agents, rust inhibitors, pH adjusters, etc. be able to.

  The drying inhibitor (wetting agent) used in the present invention is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, and acetylene. Polyhydric alcohols typified by glycol derivatives, glycerin, trimethylolpropane, etc., polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether Lower alkyl ethers, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, Methyl sulfoxide, sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives (urea, etc.). Of these, urea, glycerin, and triethylene glycol are more preferable. Moreover, said drying inhibitor may be used independently and may be used together 2 or more types. These drying inhibitors are contained in the ink in an amount of 0.5 to 50% by mass, preferably 10 to 50% by mass.

Examples of penetration enhancers used in the present invention include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. Etc. can be used.
In the present invention, glycol ether penetration enhancers such as diethylene glycol monobutyl ether and triethylene glycol monobutyl ether are preferably used.
If these are contained in the ink in an amount of 10 to 30% by mass, the effect is sufficient, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  Examples of the ultraviolet absorber used for improving the storability of the image in the present invention include JP-A Nos. 58-185677, 61-190537, JP-A-2-782, and JP-A-5-97075. Benzotriazole compounds described in JP-A-9-34057, etc., benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194443, US Pat. No. 3,214,463, etc. 48-30492, 56-21114, and cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, and 8-239368. And triazine compounds described in JP-A-10-182621, JP-A-8-501291, etc. Jar No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  In the present invention, various kinds of organic and metal complex anti-fading agents can be used as the antioxidant used to improve image storage stability. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  The antifoaming agent used in the present invention is a copolymer of dimethylpolysiloxane and polyalkylene oxide, and includes a pendant type, a terminal-modified type, an ABN type, and the like, but a pendant type is preferable. Examples of these copolymers include FZ-2203, -2207, -2222, and -2166 (trade name, manufactured by Nihon Unicar).

Antifungal agents used in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. Can be mentioned. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass.
Details of these are described in “Encyclopedia of Antibacterial and Antifungal Agents” (edited by the Japanese Association of Antimicrobial and Antifungal Society).
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite, and benzotriazole. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass.

The pH adjuster used in the present invention can be suitably used in terms of adjusting pH, imparting dispersion stability and the like, and the pH of the ink at 23 ° C. is adjusted to 8 to 11, preferably 7 to 9. It is preferable. When the pH is less than 8, the solubility of the dye is lowered and the nozzle is easily clogged, and when it exceeds 11, the water resistance tends to deteriorate. As a pH adjuster, an organic base, an inorganic alkali, etc. are mentioned as a basic thing, An organic acid, an inorganic acid, etc. are mentioned as an acidic thing.
Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, and dimethylethanolamine. Examples of the inorganic alkali include alkali metal hydroxides (for example, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (for example, sodium carbonate, sodium hydrogen carbonate, etc.), ammonium and the like. Examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like. As the pH adjuster, triethanolamine is particularly preferably used.

  The surface tension of the ink composition used in the present invention is preferably 20 to 50 mN / m or less, more preferably 20 to 40 mN / m or less at 25 ° C. for both dynamic and static surface tension. If the surface tension exceeds 50 mN / m, the ejection quality, bleeding at the time of color mixing, print quality such as whiskers, etc. will be significantly reduced. If the surface tension of the ink is 20 mN / m or less, there may be a printing failure due to ink adhesion to the hard surface during ejection.

The viscosity of the ink composition of the present invention is preferably 1 to 30 mPa · s at 25 ° C. More preferably, it is 2-15 mPa * s, Most preferably, it is 2-10 mPa * s. If it exceeds 30 mPa · s, the fixing speed of the recorded image becomes slow, and the discharge performance also deteriorates. If it is less than 1 mPa · s, the recorded image is blurred and the quality is lowered.
The viscosity can be arbitrarily adjusted by adding the ink solvent. Examples of the ink solvent include glycerin, diethylene glycol, triethanolamine, 2-pyrrolidone, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether.
A viscosity modifier may be used. Examples of the viscosity modifier include water-soluble polymers such as celluloses and polyvinyl alcohol, and nonionic surfactants. For more details, see Chapter 9 of “Viscosity Preparation Technology” (Technical Information Association, 1999), Chapter 9 and “Chemicals for Inkjet Printers (98 Supplement)-Material Development Trends and Perspective Survey” (CMC, 1997) 162- It is described on page 174.

  The ink composition of the present invention is preferably used not only for forming a single color image but also for forming a full color image. In order to form a full-color image, an ink set including a magenta ink composition, a cyan ink composition, and a yellow ink composition can be used, and a black ink composition can be further used to adjust the color tone. Good. In addition to the magenta ink composition and the cyan ink composition, a light magenta ink composition and a light cyan ink composition may be used.

  The ink set of the present invention includes the ink composition of the present invention.

In the ink set of the present invention, the magenta dye used in the magenta ink composition includes, for example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, pyrazolones, pyrazolotriazoles as coupler components Azomethine dyes having, for example, arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, oxonol dyes, etc .; methine dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc .; Examples thereof include, but are not limited to, quinone dyes such as anthrapyridone and condensed polycyclic dyes such as dioxazine dyes.
As the magenta dye, a heterocyclic azo dye is preferable, and International Patent Publication No. 2002/83795 (pages 35 to 55), 2002-83661 (pages 27 to 42), and JP-A No. 2004-149560 (paragraph number [0046]). To [0059]) and 2004-149561 (paragraph numbers [0047] to [0060]).

In the ink set of the present invention, the cyan dye used in the cyan ink composition may be, for example, an aryl or heteryl azo dye having phenols, naphthols, anilines, etc. as a coupler component; for example, phenols, naphthols, pyrrolo as a coupler component Azomethine dyes having heterocycles such as triazole; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes Indigo and thioindigo dyes can be mentioned, but are not limited thereto.
As the associative phthalocyanine dye used in the present invention, International Application Publication Nos. 2002/60994, 2003/811, 2003/62324, JP-A 2003-213167, 2004-75986, 2004-323605 No., 2004-315758, 2004-315807, and 2005-179469.

  In the ink set of the present invention, examples of the black color material that can be used in the black ink composition include disazo, trisazo, and tetraazo dyes, as well as carbon black dispersions. A preferable example is described in detail in JP-A-2005-317177.

[Ink recording method]
The recording method of the present invention is characterized by applying the ink composition of the present invention to a recording material. A preferred recording method of the present invention is an ink jet recording method, wherein recording is preferably performed by discharging droplets of the ink composition onto a recording medium, and recording is performed by supplying energy to the ink composition. Known image-receiving materials as materials, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, and JP-A-9-323475. No. 1, JP-A-62-238783, JP-A-10-153898, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947, JP-A-10-217597, -Printed paper, film, electrophotographic co-paper, cloth, glass, metal, ceramics, etc. To form. In addition, the description of Paragraph Nos. 0093 to 0105 of JP-A No. 2003-306623 can be applied as the ink jet recording method of the present invention.

In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the latex compound to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition location may be in the image receiving paper. It may be in the ink composition, or may be used as a liquid material of polymer latex alone.
Specifically, JP 2002-166638 A, JP 2002-121440 A, JP 2002-154201 A, JP 2002-144696 A, JP 2002-080759 A, JP 2002-187342 A. And the method described in JP 2002-172774 A can be preferably used.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink composition of the present invention will be described. The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheet may be used, and the thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² . The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, as the support, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

  The recording method of the present invention is not limited to the ink jet recording method, and is a known method, for example, a charge control method in which an ink composition is ejected using electrostatic attraction, and ink droplets are formed by mechanical deformation of an electrostrictive element. Drop-on-demand method (pressure pulse method) that uses the oscillating pressure of a piezo element using an inkjet head that irradiates the ink composition by converting the electrical signal into an acoustic beam and ejects the ink composition using the radiation pressure For example, a thermal ink jet method in which an ink composition is heated to form bubbles and the generated pressure is used. Inkjet recording methods include a method of ejecting many low-density ink compositions called photo inks in a small volume, a method of improving image quality using a plurality of ink compositions having substantially the same hue and different concentrations, and colorless and transparent. The method using the ink composition is included.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this. In addition, the Example using DYE-1 shall be read as a reference example.

Ultrapure water (specific resistance value: 18 MΩ · cm or more) was added to the following components to make 1 liter, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.25 μm to prepare a yellow ink liquid Y-101.
[Yellow ink Y-101 prescription]
Yellow dye (DYE-1) 50g / l
Urea 19g / l
Triethylene glycol 95g / l
Glycerin 118g / l
Triethylene glycol monobutyl ether 100g / l
2-pyrrolidone 20g / l
1,2-hexanediol 10g / l
Triethanolamine 2g / l
(Q: Is yellow triethanolamine 2 (text) or 3 (table)?)
Surfactant (W1-14) 10g / l
Proxel XL2 (Abyssia) 5g / l

  Further, light magenta ink, magenta ink, light cyan ink, cyan ink, and black ink were prepared by changing the dye type and additives, and an ink set 101 having the concentrations shown in Table 3 was prepared.

Next, the yellow ink of the ink set 101 was changed to the following yellow ink of Y-102 to Y-108, and ink sets 102 to 108 were produced.
Y-101 Yellow dye (DYE-11 (K salt) 50g / l), Surfactant (W1-14 10g / l)
Y-102 Yellow dye (DYE-11 (K salt) 50g / l), Surfactant (W1-18 10g / l)
Y-103 Yellow dye (DYE-11 (K salt) 50g / l), Surfactant (W2-13 10g / l)
Y-104 Yellow dye (DYE-12 (K salt) 50g / l), Surfactant (W2-14 10g / l)
Y-105 Yellow dye (DYE-12 (K salt) 50g / l), Surfactant (W5-3 10g / l)
Y-106 Yellow dye (Y-1 50g / l), no surfactant added
Y-107 Yellow dye (Y-1 50g / l), Surfactant (W1-14 10g / l)
Y-108 Yellow dye (Y-1 50g / l), Surfactant (W2-13 10g / l)

  The structure of the dye used is shown below.

Y-1

M-1

C-1

C-2

(Bk-1)

(Bk-2)

Further, a PM-G800 yellow ink cartridge manufactured by Epson Corporation was used as a comparative type, and ink set 109 was obtained.
These inks are loaded into the cartridge of the ink-jet printer PM-G800 manufactured by EPSON, and the image-receiving sheet has a monochrome single-color image pattern and a green, red, and gray image pattern whose density changes stepwise to EPSON CRISPIA. The image quality, ink ejection properties and image robustness were evaluated. In addition, printing was performed on copy paper Xerox 4024 (manufactured by Xerox Co., Ltd.) as plain paper, and image robustness was evaluated.

(Evaluation experiment)
1) About discharge stability, after setting a cartridge in a printer and confirming the protrusion of the ink from all the nozzles, 20 sheets of A4 were output and evaluated according to the following criteria.
A: No printing disturbance from the start to the end of printing B: Output with a disturbance in printing occurs C: Printing is disturbed from the start to the end of printing This experiment was performed immediately after ink filling (ejection A) and the ink cartridge The test was carried out after storage for 2 weeks (dischargeability B) at 40 ° C. and 80% RH.
2) The image preservability of the yellow dye was evaluated as follows by measuring the yellow density in gray using a gray image pattern.
[1] Light fastness is measured by measuring the image density Ci immediately after printing with X-rite 310, then irradiating the image with xenon light (100,000 lux) for 7 days using an Atlas weather meter, and then again image density Cf was measured and dye residual ratio (Cf / Ci) × 100 was determined and evaluated. The afterimage rate of the dye is evaluated at three points of reflection density of 0.7, 1.4, and 1.8. A is the case where the dye residual rate is 85% or more at any density, and the case of 1 point is less than 85%. B, when the two points are 85%, C, and D when the concentration of all three points is less than 85%.
[2] The heat fastness was evaluated by measuring the concentration of the sample before and after storage for 7 days at 80 ° C. and 60% RH with X-rite 310 to determine the residual ratio of the dye. The afterimage rate of the dye is evaluated at three points of reflection density of 0.7, 1.4, and 1.8. A is the case where the dye residual rate is 85% or more at any density, and the case of 1 point is less than 85%. , B was C when 2 points were less than 85%, and D was less than 85% at all concentrations.
[3] For ozone resistance, leave in a box where the ozone gas concentration is set to 5 ppm for 10 days, measure the image density before and after standing in ozone gas using a reflection densitometer (X-Rite 310TR), As evaluated. The reflection density was measured at three points of 0.7, 1.4 and 1.8. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
At any concentration, the dye residual ratio is 85% or more, A is 1 point less than 85% B, 2 points is 85% C, all concentrations are less than 85% D, 4 stages It was evaluated with.
[4] The presence or absence of occurrence of metallic luster was evaluated by visually observing the yellow and red solid print portions with reflected light. The case where the metallic luster is not observed is indicated by ○, and the case where the metallic luster is not observed is indicated by ×.
The results obtained are shown in the table below.

  From the results shown in the table, it was found that the system using the ink of the present invention is excellent in dischargeability and weather resistance and suppresses the occurrence of metallic luster.

Claims (6)

At least one compound selected from the group consisting of compounds represented by the following general formula (Y-I) and salts thereof, and at least one selected from compounds represented by the following general formulas (I) to (III): An ink composition comprising the ink composition.
Formula (Y-I):

In the formula, G represents a heterocyclic group, and n represents 2 or 3. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of
When G further has a substituent, the substituent is a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched aralkyl group having 7 to 18 carbon atoms, a linear chain having 2 to 12 carbon atoms, or Branched alkenyl group, linear or branched alkynyl group having 2 to 12 carbon atoms, linear or branched cycloalkyl group having 3 to 12 carbon atoms, linear or branched cycloalkenyl group having 3 to 12 carbon atoms, halogen Atom, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group, aryloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino Group, alkylthio group, arylthio group, alkyloxycarbonylamino group, alkylsulfonylamino group and arylsulfonylamino group, carbamoyl Group, sulfamoyl group, sulfonyl group, alkyloxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group , An aryloxycarbonyl group, an acyl group and an ionic hydrophilic group.
When R, X, Y, Z and Q are monovalent substituents, each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic ring Group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group) Arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio Group, ants Ruthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphini It represents a ruoxy group, a phosphinylamino group, a silyl group, an azo group, or an imide group, and these may further have the substituent mentioned in the G.
When R, X, Y, Z and Q are divalent substituents, each independently an alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, -O-, -CO-, —NR′— (R ′ represents a hydrogen atom, an alkyl group or an aryl group), —S—, —SO ₂ —, —SO—, —NHCH ₂ CH ₂ NH—, or —NHCONH—, Further, it may have the substituent mentioned in the G.
When R, X, Y, Z and Q are trivalent substituents, each independently represents a trivalent hydrocarbon group, a trivalent heterocyclic group,>N-,> NCH ₂ CH ₂ NH— or> Represents NCONH-.
Formula (I)

In the formula, R ₁ represents an alkyl group having 5 to 40 carbon atoms, and m ¹ , n ¹ , and o ¹ represent average addition mole numbers of ethylene oxide, propylene oxide, and butylene oxide, and are 0 to 40. . However, all of m ¹ , n ¹ , and o ¹ are not 0.
Formula (II)

In the formula, R ₂ represents an alkyl group having 5 to 40 carbon atoms, and m ² , n ² , and o ² represent average added mole numbers of ethylene oxide, propylene oxide, and butylene oxide, and are 0 to 40. . However, all of m ² , n ² , and o ² are not 0.
Formula (III)

In the formula, R ₃ and R ₄ each independently represents an alkyl group having 1 to 18 carbon atoms. R ₅ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or phenyl. m ³ , n ³ , and o ³ represent the average number of moles added of ethylene oxide, propylene oxide, and butylene oxide, respectively, and are numbers from 0 to 40. However, all of m ³ , n ³ , and o ³ are not 0. X is a hydrogen atom, or

Represents. Here, R < ₆ >, R < ₇ > represents a C1-C18 alkyl group each independently. R8 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or phenyl. m ⁴ represents the average added mole number of ethylene oxide, and m ³ + m ⁴ is a number from 0 to 100. However, when m ³ = 0, R ₅ represents a hydrogen atom, and when m ⁴ = 0, R ₈ represents a hydrogen atom. Further, when X is a hydrogen atom, ^{m 3} is a number from 1 to 100.   2. The ink composition according to claim 1, comprising 0.001 to 15% by weight of a compound represented by formulas (I) to (III).   An ink set comprising the ink composition according to claim 1.   A recording method comprising applying the ink composition according to claim 1 onto a recording medium.   4. A recording method, wherein recording is performed by discharging droplets of the ink composition according to any one of claims 1 to 3 onto a recording medium.   A recorded matter recorded using the recording method according to claim 4.