JP2015108039A - Ink composition, inkjet recording method and colored body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous black composition proving a black recording image high in color development, stable even when stored for long time, exhibiting neutral black to gray with low chroma and no color, having no change of color tone of each media and having excellent various fastness such as water resistance, weather resistance and ozone gas resistance.SOLUTION: There is provided an ink composition containing (A) a dye represented by the formula (1) and (B) carbon black.

Description

  The present invention relates to an ink composition, an ink jet recording method using the same, and a colored body.

  A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is. This method has been spreading rapidly in recent years due to the fact that the recording head is not in direct contact with the recording material and is quiet with less noise generation, and is easy to downsize and speed up. Is expected.

  Due to the recent development of inkjet technology, the improvement in printing speed in inkjet printing is remarkable. For this reason, there is a movement to use an inkjet printer in the same manner as a laser printer using electronic toner for printing a document on plain paper, which is the main use in commercial printing and office environments. Ink jet printers have the advantage that the type of recording paper is not limited and the price of the machine is relatively low. In particular, ink jet printers are spreading in small to medium office environments such as SOHO. As described above, when an inkjet printer is used for printing on plain paper, color development and water resistance tend to be more important among qualities required for printed matter. In order to satisfy these performances, a method of using a pigment ink has been proposed. In general, however, pigments tend to have poor color development and lower optical density than dyes.

  By the way, black ink is an important ink used for both mono-color and full-color images in the ink composition. However, it is technically difficult to develop a pigment that exhibits a good black color with a neutral hue between dark and light gamut, high print density, and low hue dependency on the light source. Although it is being developed, there are still few that have sufficient performance. Therefore, generally, a black ink is prepared by blending a plurality of various pigments. However, when an ink is prepared by mixing a plurality of dyes, the hue differs depending on the medium (recording material) as compared with the case where the ink is prepared with a single dye. 2) Decomposition of the dye by light or ozone gas. In particular, there is a problem that discoloration becomes large.

  As a black ink composition for inkjet having various durability of printed matter, for example, one disclosed in Patent Document 1 has been proposed. This ink composition has a very good hue as a black color, and is an ink composition in which the image fastness of the printed matter has been greatly improved. We have not yet provided products that fully satisfy the requirements of

JP-A-11-70729 Japanese Patent No. 3346755 Japanese Patent No. 4100800 International Publication No. 2010/125903 International Publication No. 2006/051850 JP 09-217081 A Japanese Patent No. 3372163

Color material, 77 [9], 417-424 [2004] (by Color Material Association, Keisuke Arai)

  The present invention has a high color developability and is stable even when stored for a long period of time, and exhibits a neutral black to gray color with low saturation and no hue in both dark and light color printing. It is an object of the present invention to provide an aqueous black ink composition that gives a black recorded image excellent in various fastness properties such as water resistance and moisture resistance.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, an ink composition in which a pigment (component (A)) represented by the following formula (1) and carbon black (component (B)) are combined is described above. The present invention has been completed by finding out that it solves the problem.

[ 式（１）中、
Ｒ^１、Ｒ^２、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子；ハロゲン原子；シアノ基；ヒドロキシ基；スルホ基；カルボキシ基；スルファモイル基；ホスホ基；ニトロ基；ウレイド基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、若しくは（Ｃ１〜Ｃ４）アルコキシ基で置換された（Ｃ１〜Ｃ４）アルキル基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、及びカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；アシル基；Ｎ−アルキルアミノスルホニル基；Ｎ−フェニルアミノスルホニル基；スルホ基、カルボキシ基、及びヒドロキシ基よりなる群から選択される少なくとも１種類以上の基で置換されたＮ−アルキルアミノスルホニル基；アルキルスルホニル基；スルホ基、カルボキシ基、及びヒドロキシ基よりなる群から選択される少なくとも１種類以上の基で置換されたアルキルスルホニル基；アシルアミノ基；アルキルスルホニルアミノ基；フェニルスルホニルアミノ基；又はハロゲン原子、（Ｃ１〜Ｃ４）アルキル基、及びニトロ基からなる群より選択される少なくとも１種類以上の基で置換されたフェニルスルホニルアミノ基；を、
Ｒ^３及びＲ^４は、それぞれ独立に、水素原子；ハロゲン原子；シアノ基；カルボキシ基；スルホ基；ニトロ基；（Ｃ１〜Ｃ４）アルキル基；ヒドロキシ基、若しくは（Ｃ１〜Ｃ４）アルコキシ基で置換された（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、及びカルボキシ基よりなる群より選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；（Ｃ１〜Ｃ４）アルキルチオ基；スルホ基、若しくはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；アシルアミノ基；アルキルスルホニルアミノ基；フェニルスルホニルアミノ基；又はハロゲン原子、（Ｃ１〜Ｃ４）アルキル基、及びニトロ基よりなる群より選択される少なくとも１種類の基で置換されたフェニルスルホニルアミノ基；を、
ｎは０または１をそれぞれ表す。]
２）
上記カーボンブラックが、表面に少なくとも1種の親水性基を、直接もしくは他の原子団を介して有する自己分散型カーボンブラックである上記１）に記載のインク組成物、
３）
式（１）において、
上記Ｒ^１乃至Ｒ^７のうち、５以上は水溶性置換基である上記１）又は２）に記載のインク組成物、
４）
式（１）において、
Ｒ^１乃至Ｒ^７のうち、３以上はスルホ基、又はカルボキシ基である、上記１）乃至３）のいずれか一項に記載のインク組成物、
５）
式（１）において、
Ｒ^１、及びＲ^２が、それぞれ独立に、水素原子；スルホ基；カルボキシ基；又はヒドロキシ基；であり、
Ｒ^３、及びＲ^４が、それぞれ独立に、水素原子；ハロゲン原子；カルボキシ基；スルホ基；スルホ基、若しくはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルコキシ基；又はスルホ基、若しくはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；であり、
Ｒ^５乃至Ｒ^７が、それぞれ独立に、水素原子；ハロゲン原子；スルホ基；カルボキシ基；ヒドロキシ基；又は（Ｃ１〜Ｃ４）アルコキシ基；であり、
ｎが１である、
上記１）乃至４）のいずれか一項に記載のインク組成物、
６）
上記式（１）において、
Ｒ^１がカルボキシ基、又はスルホ基であり、
Ｒ^２が水素原子であり、
Ｒ^３がスルホ基であり、
Ｒ^４が水素原子であり、
Ｒ^５が水素原子、カルボキシ基又はスルホ基であり、
Ｒ^６がカルボキシ基又はスルホ基であり、
Ｒ^７が水素原子であり、
ｎが１である、上記１）乃至５）のいずれか一項に記載のインク組成物、
７）
上記カーボンブラックが、表面にカルボキシ基［−ＣＯＯＭ（但し、式中のＭは水素原子、アルカリ金属、アンモニウム又は有機アンモニウムを表わす。）］を直接もしくは他の原子団を介して、少なくとも１種有する自己分散型カーボンブラックである上記１）乃至６）のいずれか一項に記載のインク組成物、
８）
上記成分（Ａ）と成分（Ｂ）の含有率の合計が３質量％以上１５質量％未満である上記１）乃至７）のいずれか一項に記載のインク組成物、
９）
インク組成物における色素分の総量中、カーボンブラックの含有率が５０質量量％以上９０質量％未満である上記１）乃至８）のいずれか一項に記載のインク組成物、
１０）
更に（Ｃ）水溶性有機溶剤を含有する上記１）乃至９）いずれか一項に記載のインク組成物、
１１）
インクジェット記録用である上記１）乃至１０）のいずれか一項に記載のインク組成物、
１２）
上記１）乃至１１）のいずれか一項に記載のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて被記録材に付着させ、記録を行うインクジェット記録方法、
１３）
被記録材が情報伝達用シートである上記１２）に記載のインクジェット記録方法、
１４）
情報伝達用シートが普通紙又は多孔性白色無機物を含むインク受容層を有するシ−トである上記１２）又は１３）に記載のインクジェット記録方法、
１５）
上記１２）乃至１４）のいずれか一項に記載のインクジェット記録方法により着色された着色体、
１６）
上記１）乃至１１）のいずれか一項に記載のインク組成物を含む容器が装填されたインクジェットプリンタ、
に関する。 That is, the present invention
1)
(A) a dye represented by the following formula (1), (B) an ink composition containing carbon black,

[In Formula (1),
R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a phospho group; a nitro group; (C1-C4) alkyl group; (C1-C4) alkoxy group; hydroxy group, or (C1-C4) alkyl group substituted with (C1-C4) alkoxy group; hydroxy group, (C1-C4) alkoxy group, (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a sulfo group and a carboxy group; an acyl group; an N-alkylaminosulfonyl group; an N-phenylaminosulfonyl group; a sulfo group; N-alkylaminosulfuryl substituted with at least one group selected from the group consisting of a carboxy group and a hydroxy group An alkylsulfonyl group; an alkylsulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group; an acylamino group; an alkylsulfonylamino group; a phenylsulfonylamino group; Or a phenylsulfonylamino group substituted with at least one group selected from the group consisting of halogen atoms, (C1-C4) alkyl groups, and nitro groups;
R ³ and R ⁴ are each independently substituted with a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; a (C1-C4) alkyl group; a hydroxy group, or a (C1-C4) alkoxy group. (C1-C4) alkyl group; (C1-C4) alkoxy group; substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group, and carboxy group (C1-C4) alkoxy group; (C1-C4) alkylthio group; (C1-C4) alkylthio group substituted by sulfo group or carboxy group; acylamino group; alkylsulfonylamino group; phenylsulfonylamino group; At least one selected from the group consisting of an atom, a (C1-C4) alkyl group, and a nitro group; And; in substituted phenylsulfonylamino group
n represents 0 or 1, respectively. ]
2)
The ink composition according to 1), wherein the carbon black is a self-dispersing carbon black having at least one hydrophilic group on a surface thereof directly or via another atomic group,
3)
In equation (1),
The ink composition according to 1) or 2), wherein 5 or more of R ^{1 to} R ⁷ are water-soluble substituents,
4)
In equation (1),
The ink composition according to any one of 1) to 3) above, wherein three or more of R ^{1 to} R ⁷ are a sulfo group or a carboxy group,
5)
In equation (1),
R ¹ and R ² are each independently a hydrogen atom; a sulfo group; a carboxy group; or a hydroxy group;
R ³ and R ⁴ are each independently a hydrogen atom; a halogen atom; a carboxy group; a sulfo group; a (C1-C4) alkoxy group substituted with a sulfo group or a carboxy group; or a sulfo group or a carboxy group. A substituted (C1-C4) alkylthio group;
R ^{5 to} R ⁷ are each independently a hydrogen atom; a halogen atom; a sulfo group; a carboxy group; a hydroxy group; or a (C1-C4) alkoxy group;
n is 1,
Ink composition as described in any one of said 1) thru | or 4),
6)
In the above formula (1),
R ¹ is a carboxy group or a sulfo group,
R ² is a hydrogen atom,
R ³ is a sulfo group,
R ⁴ is a hydrogen atom,
R ⁵ is a hydrogen atom, a carboxy group or a sulfo group,
R ⁶ is a carboxy group or a sulfo group,
R ⁷ is a hydrogen atom,
The ink composition according to any one of 1) to 5) above, wherein n is 1.
7)
The carbon black has at least one carboxy group [—COOM (wherein M represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium)] directly or via another atomic group on the surface. The ink composition according to any one of 1) to 6) above, which is self-dispersing carbon black,
8)
The ink composition according to any one of 1) to 7) above, wherein the total content of the component (A) and the component (B) is 3% by mass or more and less than 15% by mass.
9)
Ink composition as described in any one of said 1) thru | or 8) whose content rate of carbon black is 50 mass% or more and less than 90 mass% in the total amount of the pigment | dye content in an ink composition,
10)
(C) The ink composition according to any one of 1) to 9) above, which contains a water-soluble organic solvent,
11)
The ink composition according to any one of 1) to 10) above, which is for inkjet recording;
12)
An ink jet recording method in which the ink composition according to any one of 1) to 11) above is used as an ink, and ink droplets of the ink are ejected according to a recording signal to adhere to a recording material, and recording is performed;
13)
The inkjet recording method according to 12) above, wherein the recording material is an information transmission sheet,
14)
The ink jet recording method according to the above 12) or 13), wherein the information transmission sheet is a sheet having an ink receiving layer containing plain paper or a porous white inorganic substance,
15)
A colored body colored by the ink jet recording method according to any one of 12) to 14) above,
16)
An inkjet printer loaded with a container containing the ink composition according to any one of 1) to 11) above;
About.

The ink composition of the present invention has good storage stability without any change in physical properties or color after storage for a long period of time. In addition, the ink composition of the present invention is used for inkjet recording, writing instruments, etc., and when the ink of a recorded image has a neutral hue and a low pigment concentration when recorded on plain paper and inkjet dedicated paper However, a printed matter with a black hue can be obtained. In addition, the print density is high, and it is excellent in moisture resistance, ozone gas resistance, light resistance, water resistance, and near infrared light sensor compatibility.
Further, when used together with magenta, cyan and yellow dyes, full color ink jet recording excellent in high color development, light resistance, ozone gas resistance and water resistance is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

The present invention will be described in detail.
The ink composition of the present invention contains a dye represented by the above formula (1) as the component (A). This compound can be obtained by the method described in Japanese Patent No. 4164829.

In the above formula (1), R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; A nitro group; a ureido group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group, or a (C1-C4) alkyl group substituted with an alkoxy group; a hydroxy group; (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of an alkoxy group, a sulfo group, and a carboxy group; an acyl group; an N-alkylaminosulfonyl group; an N-phenyl group An aminosulfonyl group; substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group; An alkylsulfonyl group; an alkylsulfonyl group; an alkylsulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group; an acylamino group; an alkylsulfonylamino group; An amino group; or a phenylsulfonylamino group substituted with at least one group selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, and a nitro group.

In the above formula (1), examples of the halogen atom in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. An atom is preferable and a fluorine atom and a chlorine atom are more preferable.

In the above formula (1), examples of the (C1-C4) alkyl group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include a linear or branched unsubstituted group. Those are preferred. Specific examples thereof include, for example, a linear group such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group; a branched chain such as an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group; Is mentioned. Preferable specific examples include a methyl group and an n-propyl group, and a methyl group is more preferable.

In the above formula (1), examples of the (C1-C4) alkoxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include those in which the alkyl moiety is a linear or branched unsubstituted group, A straight chain is preferred. Specific examples thereof include, for example, straight chain such as methoxy group, ethoxy group, n-propoxy group, and n-butoxy group; branched chain such as isopropoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group; Etc. Preferably, a methoxy group, an ethoxy group, and n-propoxy group are mentioned, A methoxy group is more preferable.

In the above formula (1), the (C1-C4) alkyl group substituted with a hydroxy group or a (C1-C4) alkoxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ includes the above ( A C1-C4) alkyl group in which any one or both of a hydroxy group and a (C1-C4) alkoxy group are substituted is mentioned. The substitution position of the hydroxy group or the (C1 to C4) alkoxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitutions is 1 or 2, preferably 1. In the said (C1-C4) alkoxy group, the same thing is mentioned including the said (C1-C4) alkoxy group, a specific example, a preferable thing, and a more preferable thing. Specific examples of the hydroxy group or the (C1-C4) alkyl group substituted with a (C1-C4) alkoxy group include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, a 4-hydroxy group. -N-butyl group, methoxymethyl group, 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, ethoxymethyl group, 2-ethoxyethyl group, 3-ethoxy-n- Propyl group, 4-ethoxy-n-butyl group, n-propoxymethyl group, 2- (n-propoxy) ethyl group, 3- (n-propoxy) -n-propyl group, 4- (n-propoxy) -n -Butyl group, (n-butoxy) methyl group, 2- (n-butoxy) ethyl group, 3- (n-butoxy) -n-propyl group, 4- (n-butoxy) -n-butyl group And the like.

In the above formula (1), at least one selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ . The (C1 to C4) alkoxy group substituted with the group is selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group, and a carboxy group on the carbon atom of the (C1 to C4) alkoxy group. And at least one kind of group substituted. The substitution position of the hydroxy group, (C1-C4) alkoxy group, sulfo group, or carboxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitutions is 1 or 2, preferably 1. Examples of the (C1 to C4) alkoxy group as a substituent include the above (C1 to C4) alkoxy groups and specific examples, preferable ones, and more preferable ones. Specific examples of the (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group include a hydroxymethoxy group, a hydroxy group Substituted with a hydroxy group such as ethoxy group, hydroxy-n-propoxy group, hydroxy-n-butoxy group; methoxymethoxy group, methoxyethoxy group, methoxy-n-propoxy group, methoxy-n-butoxy group, ethoxymethoxy Group, ethoxyethoxy group, ethoxy-n-propoxy group, ethoxy-n-butoxy group, (n-propoxy) methoxy group, (n-propoxy) ethoxy group, (n-propoxy) -n-propoxy group, (n- Propoxy) -n-butoxy group, (n-butoxy) methoxy group, (n-butoxy) Toxi group, (n-butoxy) -n-propoxy group, (n-butoxy) -n-butoxy group, isopropoxymethoxy group, isopropoxyethoxy group, isopropoxy-n-propoxy group, isopropoxy-n-butoxy group , (Tert-butoxy) methoxy group, (tert-butoxy) ethoxy group, (tert-butoxy) -n-propoxy group, (tert-butoxy) -n-butoxy group and the like (C1-C4) alkoxy groups. Substituted with a sulfo group such as sulfomethoxy group, sulfoethoxy group, sulfo-n-propoxy group, sulfo-n-butoxy group; carboxymethoxy group, carboxyethoxy group, carboxy-n-propoxy group, carboxy Substituted with a carboxy group such as -n-butoxy group; and sulfo-n Propoxy group, a sulfo -n- butoxy group, a carboxy -n- propoxy group, a carboxy -n- butoxy group are preferable, sulfo -n- propoxy group, a sulfo -n- butoxy group are more preferable.

In the above formula (1), examples of the acyl group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include an alkylcarbonyl group, a phenylcarbonyl group (benzoyl group), an aldehyde group, or an amide group. . Examples of the alkylcarbonyl group include those in which the alkyl moiety is linear or branched, and linear is preferable. Specific examples thereof include, for example, linear groups such as an acetyl group (methylcarbonyl group), propionyl group (ethylcarbonyl group), n-propylcarbonyl group, n-butylcarbonyl group; isopropylcarbonyl group, isobutylcarbonyl group, sec -Branched ones such as a butylcarbonyl group and a pivaloyl group (tert-butylcarbonyl group); a straight-chain one is preferable and an acetylamino group is more preferable. As the acyl group, an alkylcarbonyl group and a benzoyl group are preferable, and an acetyl group is more preferable.

In the above formula (1), as the N-alkylaminosulfonyl group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , the alkyl moiety is a (C1 to C8) alkyl group, preferably (C1 to C6). ) An alkyl group, more preferably a (C1-C4) alkyl group, and the same as the above (C1-C4) alkyl group and specific examples, preferable ones, and more preferable ones. Specific examples of the N-alkylaminosulfonyl group include N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N- (n-propyl) aminosulfonyl group, N- (n-butyl) aminosulfonyl group, N- And isopropylaminosulfonyl group, N- (tert-butyl) aminosulfonyl group, and the like. N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N- (n-propyl) aminosulfonyl group, N- (n- (Butyl) aminosulfonyl group is preferable, and N-methylaminosulfonyl group and N-ethylaminosulfonyl group are more preferable.

In the above formula (1), N substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ Examples of the -alkylaminosulfonyl group include those in which at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group is substituted on the carbon atom of the alkyl part of the N-alkylaminosulfonyl group. It is done. The substitution position is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitution is usually 1 to 3, preferably 1. Specific examples of the N-alkylaminosulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group include an N-sulfomethylaminosulfonyl group, N- (2 Substituted with a sulfo group such as -sulfoethyl) aminosulfonyl group, N- (3-sulfo-n-propyl) aminosulfonyl group, N- (4-sulfo-n-butyl) aminosulfonyl group; N-carboxymethyl A carboxy group such as an aminosulfonyl group, N- (2-carboxyethyl) aminosulfonyl group, N- (3-carboxy-n-propyl) aminosulfonyl group, N- (4-carboxy-n-butyl) aminosulfonyl group; Substituted: N-hydroxymethylaminosulfonyl group, N- (2-hydroxyethyl) aminosulfur Substituted with a hydroxy group such as a nyl group, an N- (3-hydroxy-n-propyl) aminosulfonyl group, an N- (4-hydroxy-n-butyl) aminosulfonyl group, a sulfo group, or Those substituted with a carboxy group are preferred, and an N- (2-sulfoethyl) aminosulfonyl group and an N- (2-carboxyethyl) aminosulfonyl group are more preferred.

In the above formula (1), as the alkylsulfonyl group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , the alkyl part is a (C1-C8) alkyl group, preferably a (C1-C6) alkyl group. More preferably, it is a (C1-C4) alkyl group, and the same as the above (C1-C4) alkyl group and specific examples, preferable ones, and more preferable ones. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, and an n-butylsulfonyl group.

In the above formula (1), alkyl substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ Examples of the sulfonyl group include those in which at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group is substituted on the carbon atom of the alkyl portion of the alkylsulfonyl group. Although the substitution position is not particularly limited, it is preferably substituted at the end of the alkyl group, and the number of substitution is usually 1 to 3, preferably 1 or 2. Specific examples of the alkylsulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group include a sulfomethylsulfonyl group, a 2-sulfoethylsulfonyl group, and a 3-sulfo group. Substituted with a sulfo group such as -n-propylsulfonyl group, 4-sulfo-n-butylsulfonyl group; carboxymethylsulfonyl group, 2-carboxyethylsulfonyl group, 3-carboxy-n-propylsulfonyl group, 4- Substituted with a carboxy group such as carboxy-n-butylsulfonyl group; such as hydroxymethylsulfonyl group, 2-hydroxyethylsulfonyl group, 3-hydroxy-n-propylsulfonyl group, 4-carboxy-n-butylsulfonyl group, etc. Substituted with a hydroxy group; E group preferably substituted with a carboxy group, 2-sulfoethyl sulfonyl group, 2-carboxyethyl sulfonyl group is more preferable.

In the above formula (1), examples of the acylamino group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include those in which the acyl group is substituted on the amino group. Group (benzoylamino group) and the like. Specific examples of the alkylcarbonylamino group include linear ones such as acetylamino group (methylcarbonylamino group), propionylamino group (ethylcarbonylamino group), n-propylcarbonylamino group, and n-butylcarbonylamino group. Branched chain groups such as isopropylcarbonylamino group, isobutylcarbonylamino group, sec-butylcarbonylamino group, pivaloylamino group (tert-butylcarbonylamino group), and the like. More preferred. As the acylamino group, an alkylcarbonylamino group and a benzoylamino group are preferable, and an acetylamino group and a benzoylamino group are more preferable.

In the above formula (1), as the alkylsulfonylamino group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , the alkyl part is a (C1-C8) alkyl group, preferably (C1-C6) alkyl. Groups, more preferably those which are (C1-C4) alkyl groups, and the same as the above (C1-C4) alkyl groups and specific examples, preferred ones and more preferred ones. Specific examples of the alkylsulfonylamino group include methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group, n-butylsulfonylamino group, isopropylsulfonylamino group, tert-butylsulfonylamino group, and the like. A methylsulfonylamino group, an ethylsulfonylamino group, an n-propylsulfonylamino group, and an n-butylsulfonylamino group are preferable, and a methylsulfonylamino group and an ethylsulfonylamino group are more preferable.

In the above formula (1), at least one group selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, and a nitro group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ Examples of the substituted phenylsulfonylamino group include those in which at least one group selected from the group consisting of a halogen atom, a (C1 to C4) alkyl group, and a nitro group is substituted on the carbon atom of the phenylsulfonylamino group. It is done. Although it does not restrict | limit especially as a substitution position of at least 1 type of group selected from the group which consists of a halogen atom, a (C1-C4) alkyl group, and a nitro group, It substitutes by carbon atoms other than the carbon atom couple | bonded with the sulfur atom. And the number of substitution is usually 1 to 3, preferably 1 or 2, and more preferably 1. Examples of the halogen atom include the above-mentioned halogen atoms and specific examples, preferable ones, and more preferable ones, and (C1-C4) alkyl groups include the above-mentioned (C1-C4) alkyl groups and specific examples, preferably. And the like, including the more preferable ones. Specific examples of the phenylsulfonylamino group substituted with at least one group selected from the group consisting of a halogen atom, a (C1 to C4) alkyl group, and a nitro group include a 2-chlorophenylsulfonylamino group, 3- Substituted with halogen atoms such as chlorophenylsulfonylamino group, 4-chlorophenylsulfonylamino group, 2-bromophenylsulfonylamino group, 4-fluorophenylsulfonylamino group; 2-methylphenylsulfonylamino group, 3-methylphenylsulfonyl (C1-C4) alkyl such as amino group, 4-methylphenylsulfonylamino group, 2-ethylphenylsulfonylamino group, 3- (n-propyl) phenylsulfonylamino group, 4- (n-butyl) phenylsulfonylamino group Substituted with groups Substituted with a nitro group such as a 2-nitrophenylsulfonylamino group, a 3-nitrophenylsulfonylamino group, a 4-nitrophenylsulfonylamino group; Are preferable, and 4-methylphenylsulfonylamino group is more preferable.

In Formula (1), R ³ and R ⁴ each independently represent a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; a (C1-C4) alkyl group; a hydroxy group, or (C1- C4) (C1-C4) alkyl group substituted with an alkoxy group; (C1-C4) alkoxy group; at least one selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group, and carboxy group (C1-C4) alkoxy group substituted with various groups; (C1-C4) alkylthio group; (C1-C4) alkylthio group substituted with sulfo group or carboxy group; acylamino group; alkylsulfonylamino group; phenyl A sulfonylamino group; or selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, and a nitro group Without even phenylsulfonyl amino group substituted with one or more groups; represents a.

In the formula (1), the halogen atom in R ³ and R ⁴ is the same as the halogen atom in the above R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , including specific examples, preferred ones, and more preferred ones. Things.

In the formula (1), as the (C1-C4) alkyl group in R ³ and R ^4, the (C1-C4) alkyl group in the above R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , specific examples, The same thing is mentioned including a preferable thing and a more preferable thing.

In the formula (1), as the hydroxy group in R ³ and R ⁴ or the (C1-C4) alkyl group substituted with the (C1-C4) alkoxy group, the above R ¹ , R ² , R ⁵ , R ⁶ and The hydroxy group in R ⁷ or the (C1-C4) alkyl group substituted with a (C1-C4) alkoxy group, and specific examples, preferable ones, and more preferable ones are exemplified.

In formula (1), as the (C1-C4) alkoxy group in R ³ and R ^4, the (C1-C4) alkoxy group in the above R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , specific examples, The same thing is mentioned including a preferable thing and a more preferable thing.

In formula (1), substituted with at least one group selected from the group consisting of a hydroxy group in R ³ and R ⁴ , a (C 1 -C ⁴ ) alkoxy group, a sulfo group, and a carboxy group (C 1 -C ⁴ ). The alkoxy group is at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, or a carboxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ . (C1-C4) alkoxy groups substituted with and specific examples, preferred ones, and more preferred ones.

In formula (1), examples of the (C1 to C4) alkylthio group in R ³ and R ⁴ include those in which the alkyl part is linear or branched, and linear is preferable. Specific examples include straight chain groups such as methylthio group, ethylthio group, n-propylthio group, and n-butylthio group; branched chain groups such as isopropylthio group, isobutylthio group, sec-propylthio group, and tert-butylthio group; A straight chain is preferable, and a methylthio group is more preferable.

In the formula (1), as the (C1-C4) alkylthio group substituted with a sulfo group or a carboxy group in R ³ and R ⁴ , these substitutions are made on any carbon atom in the (C1-C4) alkylthio group The thing which has group is mentioned. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited, but is preferably substituted with a carbon atom other than the carbon atom to which the sulfur atom in the alkylthio group is bonded. Specific examples thereof include those substituted with a sulfo group such as 2-sulfoethylthio, 3-sulfo-n-propylthio, 4-sulfo-n-butylthio group, etc .; 2-carboxyethylthio, 3-carboxy- those substituted with a carboxy group such as n-propylthio, 4-carboxy-n-butylthio and the like, and those substituted with a sulfo group are preferred, and a 3-sulfopropylthio group is particularly preferred.

In the formula (1), the acylamino group in R ³ and R ⁴ is the same as the acylamino group in the above R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , including specific examples, preferred ones and more preferred ones. Things.

In formula (1), as the alkylsulfonylamino group in R ³ and R ^4, the alkylsulfonylamino group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , specific examples, preferable ones, and more preferable ones. The same thing is mentioned including.

In the formula (1), as the phenylsulfonylamino substituted with at least one group selected from the group consisting of a halogen atom in R ³ and R ⁴ , a (C1-C4) alkyl group, and a nitro group, Phenylsulfonylamino substituted with at least one group selected from the group consisting of a halogen atom in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , a (C1-C4) alkyl group, and a nitro group; Specific examples, preferable ones, and more preferable ones are also included.

In formula (1), preferred as R ¹ and R ² is a case where either one is a hydrogen atom or a sulfo group, and the other is a carboxyl group, a sulfo group or a (C1-C4) alkoxy group, and more preferred. Is the case where either one is a hydrogen atom and the other is a carboxy group or a sulfo group.
Preferred as R ³ and R ⁴ is the case where one is a sulfo group, a carboxy group, or a sulfo (C1-C4) alkoxy group, and the other is a hydrogen atom, a sulfo group, or a (C1-C4) alkyl group, More preferably, one is a sulfo group and the other is a hydrogen atom.
Any one of R ⁵ , R ⁶ and R ⁷ is preferably a sulfo group, a carboxy group, a (C1-C4) alkoxy group, or a halogen atom, and a sulfo group is more preferable.
n may be 0 or 1, but 1 is more preferable.

One of the preferred embodiments of the present invention is a case where 5 or more of R ¹ to R ⁷ are water-soluble substituents.
A case where 3 or more is a sulfo group or a carboxy group is also a preferred embodiment, and 5 or more are water-soluble substituents, and 3 or more of them are a sulfo group or a carboxy group, most preferably.

Among the above R ¹ to R ⁷ , a compound in which preferred ones are combined is more preferable, and a compound in which more preferable ones are combined is more preferable. The same applies to combinations of preferable and more preferable ones.

  Specific examples of the dye represented by the above formula (1) are shown in Tables 1 to 3 below. However, it is not limited to these.

  Of these, the dye of Compound No. 1 is particularly preferred.

The ink composition of the present invention contains carbon black as the component (B). Carbon black can synergistically improve the color developability of the above formula (1), and can further improve various fastnesses such as water resistance, moisture resistance and ozone gas resistance.
Examples of the carbon black (CI pigment black 7) used in the present invention include acetylene black, channel black, furnace black, and lamp black. Specific examples of the carbon black, for example Raven760ULTRA, Raven780ULTRA, Raven790ULTRA, Raven1060ULTRA, Raven1080ULTRA, Raven1170, Raven1190ULTRA II, Raven1200, Raven1250, Raven1255, Raven1500, Raven2000, Raven2500ULTRA, Raven3500, Raven5000ULTRA II, Raven5250, Raven5750, Raven7000 (Columbia (Manufactured by Carbon); Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 300, Monarch 1400, Regal 1330R, Regal 1400R, Regal 1660R, Mogul L (manufactured by Cabot Corporation); Color Black FW1, Color Black FW 2, 160 Black, FW, S U, Printex V, Printex 140U, Printex 140V, SpecIal Black 4, SpecIal Black 4A, SpecIal Black 5, Special Black 6 (manufactured by Degussa); # 2700B, # 26 # 50, B26 B, # 2400B, # 2350, # 2300, # 2300B, # 2200B, # 1000, # 1000B, # 990, # 990B, # 980, # 980B, # 970, # 960, # 960B, # 950, # 950B, # 900, # 900B, # 850, # 850B, # 650B, # 52, # 52B, # 50, # 47, # 47B, # 45, # 45B, # 45L, # 44, # 44B, # 40, # 40B , # 33, # 33B, # 32, # 32B, # 30, # 30B, # 25, # 25B, # 20, # 20B, # 10, # 10B, # 5, # 5B, # 95, MA7, MA8, MA100, MA600, MCF-88, No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300 (manufactured by Mitsubishi Chemical Corporation);

  As a preferred embodiment of the present invention, it is preferable to add to the ink as a pigment dispersion obtained by dispersing in an aqueous solvent. Carbon blacks other than channel black are very difficult to disperse in water as they are. Therefore, a method of dispersing using a surfactant or a method of chemically modifying the surface of carbon black to make it hydrophilic to form a self-dispersing carbon black has been proposed (Non-Patent Document 1). In the present invention, it does not matter which carbon black is dispersed in any form, but it is more preferable to use a self-dispersing carbon black having a long-term storage stability and a high storage stability against a temperature change.

The self-dispersing carbon black has at least one hydrophilic group on its surface, directly or via another atomic group. This improves dispersibility in water, alcohol, and the like.
Examples of the hydrophilic group include a sulfo group (—SO ₃ M), a carboxy group (—COOM), a phosphate group (—PO ₃ M ₂ ), and the like, but a sulfo group (—SO ₃ H). A carboxy group (—COOM) is preferred, and a carboxy group (—COOM) is the most preferred embodiment. Here, M represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium, preferably a hydrogen atom, an alkali metal, or ammonium, and particularly preferably an alkali metal.

  In the ink composition of the present invention, the total content of component (A) and component (B) is preferably 3% by mass or more and less than 15% by mass, and more preferably 5% by mass or more and less than 10% by mass. preferable.

  Further, in the total amount of the coloring matter in the ink composition of the present invention, the carbon black content is preferably 50% by mass or more and less than 90% by mass, and more preferably 60% by mass or more and less than 80% by mass.

The dye represented by the above formula (1) can also be used as a free acid or a salt thereof. Examples of the compound salt represented by the above formula (1) include salts with inorganic or organic cations. Specific examples of the inorganic cation salt include alkali metal salts such as lithium salts, sodium salts, potassium salts and the like; and ammonium salts (NH ₄ ⁺ ). Examples of the organic cation include, but are not limited to, quaternary ammonium represented by the following formula (2).

In the above formula (2), Z ^{1 to} Z ⁴ are each independently a hydrogen atom, a (C1 to C4) alkyl group, a hydroxy (C1 to C4) alkyl group, or a hydroxy (C1 to C4) alkoxy (C1 to C4) alkyl. Represents a group, and at least one of Z ^{1 to} Z ⁴ is a group other than a hydrogen atom.

Here, examples of the (C1-C4) alkyl group in Z ^{1 to} Z ⁴ include methyl, ethyl and the like. Similarly, examples of the hydroxy (C1-C4) alkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. It is done. Similarly, examples of the hydroxy (C1-C4) alkoxy (C1-C4) alkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2 -(Hydroxyethoxy) butyl etc. are mentioned.

  Among the above salts, preferred are alkali metal salts such as sodium, potassium and lithium; organic quaternary ammonium salts such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine salts; Ammonium salt; and the like. Of these, lithium salts, sodium salts, and ammonium salts are more preferable.

As will be apparent to those skilled in the art, the salt or free acid of the compound represented by the above formula (1) can be easily obtained by the following method or the like.
For example, in the synthesis reaction of the compound of formula (1), the reaction solution after completion of the final step, or an aqueous solution containing a salt of the compound of formula (1), for example, water-soluble organics such as acetone and (C1-C4) alcohol The sodium salt of the compound of the above formula (1) can be obtained as a wet cake by separating the solid precipitated by a method of adding a solvent; a method of salting out by adding sodium chloride;
Further, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration, whereby the free acid of the compound of the above formula (1) is obtained. Or a mixture of a free acid and a sodium salt in which a part of the compound of the formula (1) is a sodium salt.
Also, after dissolving the obtained sodium salt wet cake or its dry solid in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added to adjust the pH appropriately, for example, to pH 1 to 3, By separating the precipitated solid by filtration, an ammonium salt of the compound of the above formula (1) can be obtained. A mixture of an ammonium salt of the compound of formula (1) and a sodium salt of the compound of formula (1) by appropriately adjusting the amount or / and pH of ammonium chloride to be added; or the free acid of the compound of formula (1) And a mixture of ammonium salts;
Further, as described later, a free acid solid can be directly obtained by adding a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) to the reaction solution after completion of the above reaction. In this case, the wet cake of the free acid of the compound of formula (1) is added to water and stirred, for example, potassium hydroxide; lithium hydroxide; ammonia water; or water of organic quaternary ammonium of formula (2) By adding an oxide; etc. to form a salt, a potassium salt, a lithium salt, an ammonium salt, or a quaternary ammonium salt according to each added compound can be obtained. By limiting the number of moles of the above-mentioned hydroxide to be added with respect to the number of moles of free acid, for example, a mixed salt of lithium salt and sodium salt, etc .; and a mixture of lithium salt, sodium salt, and ammonium salt Salts and the like can also be prepared. The salt of the compound of the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the intended ink performance.

  After completion of the reaction, the compound represented by the above formula (1) can be isolated as a solid free acid by adding a mineral acid such as hydrochloric acid, and the resulting free acid solid is water or, for example, hydrochloric acid water or the like. By washing with acidic water, inorganic salts (inorganic impurities) contained as impurities, such as sodium chloride and sodium sulfate, can be removed. As described above, the free acid of the compound of the present invention obtained as described above is obtained by treating the obtained wet cake or its dried solid with a desired inorganic or organic base in water to give a salt of the corresponding compound. Solution. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and ammonium hydroxide (ammonia water). And the like. Examples of the organic base include, but are not limited to, organic amines corresponding to the quaternary ammonium represented by the above formula (2), for example, alkanolamines such as diethanolamine and triethanolamine.

In addition to the azo compound of the present invention, the ink composition of the present invention may appropriately contain other toning pigments and the like for the purpose of adjusting the subtle hue of black. Even in such a case, the total mass of the pigment contained in the ink composition of the present invention may be in the above range with respect to the total mass of the ink composition.
Examples of toning dyes include yellow (for example, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 161, etc. ), Orange (for example, CI Direct Orange 17, CI Direct Orange 26, CI Direct Orange 29, CI Direct Orange 39, CI Direct Orange 49, etc.), Brown, Scarlet (E.g., CI Direct Red 89), red (e.g., CI Direct Red 62, CI Direct Red 75, CI Direct Red 79, CI Direct Red 80, CI Direct Red 84, CI Direct Red 225, CI Direct Red 226), magenta (for example, CI Direct Red 227), violet, blue, navy, cyan (for example, CI Direct Blue 199, CI Acid Blue 249, etc.), green (for example, Acid Green 1) ), Black (for example, CI Acid Black 2), and other dyes having various hues.

The ink composition of the present invention is prepared using water as a medium, and may contain a water-soluble organic solvent (an organic solvent miscible with water) (component (C)) as long as the effects of the present invention are not impaired. . This water-soluble organic solvent dissolves the dye; prevents the composition from drying (maintains a wet state); adjusts the viscosity of the composition; promotes penetration of the dye into the recording material; adjusts the surface tension of the composition; An effect such as defoaming of the composition can be expected, and the ink composition of the present invention is preferably contained.
The water-soluble organic solvent (component (C)) used in the preparation of the water-based ink composition is not particularly limited. For example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, second butanol (C1-C4) alkanols such as tributanol, carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide, lactams such as 2-pyrrolidone and N-methylpyrrolidin-2-one, 1,3- Cyclic ureas such as dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one, ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one , Cyclic ethers such as tetrahydrofuran and dioxane Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, pentamethylene glycol, 1,6-hexylene glycol, 1,2-hexylene glycol , Monomers having (C2-C6) alkylene units such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol, oligomers or polyalkylene glycols or thioglycols, Polyol (triol) such as glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether (C1-C4) alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol) or triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, γ-butyrolactone or dimethyl sulfoxide Etc. can be used.
The water-soluble organic solvent is preferably one or two or more water-soluble organic solvents selected from the group consisting of 2-pyrrolidone, glycerin solvents, and glycol solvents.
The glycerin-based solvent is an aliphatic hydrocarbon or ether in which a hydroxyl group is substituted on three carbon atoms. Among the above examples, polyols (triols) such as glycerin and hexane-1,2,6-triol. ) Etc. correspond to this.
Glycol solvents are aliphatic hydrocarbons or ethers in which two carbon atoms are substituted with hydroxy groups. Among the above examples, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol 1,2-butylene glycol, 1,4-butylene glycol, pentamethylene glycol, 1,6-hexylene glycol, 1,2-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene Monomers, oligomers or polyalkylene glycols or thioglycols having (C2 to C6) alkylene units such as glycol, polypropylene glycol, thiodiglycol, dithiodiglycol, glycerin, hexane-1,2,6 Polyols such as triols (triol), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, or triethylene glycol monoethyl ether (C1 to C4) alkyl ethers of the polyhydric alcohols fall under this category.
Of these, 2-pyrrolidone, glycerin, pentamethylene glycol, and 1,2-hexylene glycol are more preferable, and 2-pyrrolidone, glycerin, ethylene glycol, pentamethylene glycol, and 1,2-hexylene glycol are more preferable. It is. These organic solvents may be used alone or in combination of two or more.

  The water-soluble organic solvent includes a substance that is solid at room temperature, such as trimethylolpropane. However, even if the substance or the like is solid, it shows water solubility, and an aqueous solution containing the substance or the like shows the same properties as the water-soluble organic solvent and can be used with the expectation of the same effect. Therefore, in this specification, for the sake of convenience, such a solid substance is included in the category of a water-soluble organic solvent as long as it can be used in expectation of the same effect as described above.

  The preferable content of the water-soluble solvent is 0 to 50% by mass, more preferably 15 to 50% by mass, based on the total amount of the water-based ink composition of the invention.

 The ink composition of the present invention may further contain an ink adjusting agent for the purpose of improving the storage stability of the ink composition. Examples of the ink adjusting agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventing agents, water-soluble UV absorbers, water-soluble polymer compounds, dye dissolving agents, antioxidants, surfactants, antifoaming agents. Agents and the like.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the coloring composition in an amount of 0.02 to 1.00% by mass.

  Examples of preservatives include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, and benzothiazole. , Isothiazoline, dithiol, pyridine oxyd, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl bromide Acetate-based and inorganic salt-based compounds are exemplified. Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine oxido compound include sodium 2-pyridinethiol-1-oxide, and examples of the inorganic salt compound include anhydrous sodium acetate. Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned. Other antiseptic / antifungal agents include sodium sorbate, sodium benzoate and the like.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the prepared ink. Examples include alkanolamines such as diethanolamine, triethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide (ammonia), or lithium carbonate. And alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate, and inorganic bases such as potassium acetate, sodium silicate and disodium phosphate.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

  Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

  Examples of the dye solubilizer include ε-caprolactam, ethylene carbonate, urea and the like. In particular, when urea is contained, it is one of the preferred embodiments of the present invention.

  As the antioxidant, for example, various organic and metal complex antifading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, and the like.

Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants. Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfate polys. Oxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkyl allyl sulfone hydrochloride, diethyl sulfo Examples thereof include oxalate, diethylhexylsilsulfosuccinate, dioctylsulfosuccinate and the like. Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyallylalkyl. Ethers such as alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate Esters, polyoxyethylene stearate, 2,4,7,9-tetramethyl-5-decyne-4,7-di Lumpur, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3 acetylene glycol such as ol (e.g., manufactured by Nissin Chemical Industry Co., Ltd. Surfynol ^RTM 104 and 105 , 82, 420, 440, 465, Olfine ^RTM STG, etc.). Of these, Surfynol ^RTM 420, 440 and 465 are preferably used, and Surfynol ^RTM 440 is particularly preferably used. In the present specification, the superscript “RTM” means a registered trademark.
Etc.

  Examples of antifoaming agents include highly oxidized oils, glycerin fatty acid esters, fluorines, and silicone compounds.

  These ink preparation agents are used alone or in combination. The surface tension of the ink composition of the present invention is usually 25 to 70 mN / m, preferably 25 to 60 mN / m, and the viscosity is preferably 30 mPa · s or less, more preferably 20 mPa · s or less.

  In the production of the aqueous ink composition of the present invention, there is no particular limitation on the order of dissolving each agent such as an additive. The water used for preparing the ink composition is preferably water with few impurities such as ion exchange water and distilled water. Further, if necessary, after the ink composition is prepared, fine filtration may be performed using a membrane filter or the like to remove impurities in the ink composition. In particular, when the ink composition of the present invention is used as an ink for ink jet recording, it is preferable to perform microfiltration.

  The ink composition containing the compound of the present invention is suitable for use in printing, copying, marking, writing, drawing, stamping, or recording (printing), particularly in inkjet recording. In addition, the ink composition of the present invention is less likely to precipitate solids even when dried in the vicinity of the nozzles of the recording head of an ink jet printer, and for this reason, the recording head is also less likely to block.

  Next, the ink jet recording method of the present invention will be described. The inkjet recording method of the present invention is characterized in that recording is performed using the aqueous ink composition of the present invention as an inkjet ink. In the ink jet recording method of the present invention, recording is performed on an image receiving material using the aqueous ink composition of the present invention, but there are no particular limitations on the ink nozzles and the like used at that time, and they may be appropriately selected according to the purpose. Known methods, for example, a charge control system that ejects ink using electrostatic attraction, a drop-on-demand system (pressure pulse system) that uses the vibration pressure of a piezo element, and an electrical signal is converted into an acoustic beam. Use an acoustic ink jet system that irradiates ink and ejects ink using radiation pressure, a thermal ink jet (bubble jet (registered trademark)) system that uses ink to form bubbles by heating the ink, and the like. Can do. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent. A method using ink is included.

  The colored product of the present invention is colored with the above-described aqueous ink composition of the present invention, and more preferably is colored with an ink jet printer using the aqueous ink composition of the present invention. Examples of materials that can be colored include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and base materials for color filters. The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. For the ink-receiving layer, for example, a porous white inorganic substance capable of absorbing the pigment in the ink such as porous silica, alumina sol, and special ceramics by impregnating or coating the above-mentioned base material with a cationic polymer is used. It is provided by coating the surface of the substrate together with a hydrophilic polymer such as polyvinylpyrrolidone. A paper provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film), etc., for example, as a typical commercial product, Pictorico (Asahi Glass Co., Ltd.), professional photo paper, Super photo paper, matte photo paper, glossy gold, platinum grade (all manufactured by Canon Inc.), photo paper (gloss), photo matte paper, photo paper Crispia (high gloss) (all manufactured by Seiko Epson Corp.) , Premium Plus Photo Paper, Premium Glossy Film, Photo Paper, Advanced Photo Paper (all manufactured by Hewlett-Packard Japan), Photo-like QP (manufactured by Konica Corporation), Painting Photo Finishing Pro (Fuji Film Co., Ltd.) )) Etc. Of course, plain paper, high-quality paper, and coated paper can also be used.

  Among these, it is known that an image recorded on a recording material coated with a porous white inorganic substance on the surface is particularly prone to discoloration by ozone gas, but the aqueous ink composition of the present invention is also resistant to ozone gas. Since it is excellent, it is also effective when recording on such a recording material.

  In order to record on the recording material by the ink jet recording method of the present invention, for example, a container containing the above ink composition may be set at a predetermined position of the ink jet printer and recorded on the recording material by a normal method. . In the ink jet recording method of the present invention, a black ink composition of the present invention, a publicly known magenta ink composition, a cyan ink composition, a yellow ink composition, and a green ink composition, blue (or violet) as necessary. Used in combination with an ink composition and a red (or orange) ink composition. The ink composition of each color is poured into each container, and the container is used by being loaded into a predetermined position of the ink jet printer in the same manner as the container containing the aqueous ink composition for ink jet recording of the present invention. Examples of the ink jet printer include a piezo printer using mechanical vibration and a bubble jet (registered trademark) printer using bubbles generated by heating.

The water-based ink composition of the present invention is a black recorded image of an ideal hue that is very clear on a recording material such as plain paper and an information transmission sheet having an ink receiving layer, has a high print density, and low saturation. give. Therefore, it is also possible to faithfully reproduce a photographic color image on paper. In addition, the aqueous ink composition of the present invention has very good storage stability without solid precipitation, physical property change, hue change, etc. after long-term storage.
The water-based ink composition of the present invention is used for inkjet recording and writing instruments, and even when used as an inkjet ink, solid precipitation due to drying of the ink composition in the vicinity of the nozzle is very unlikely to occur, and an ejector (recording head). There is no blockage. In addition, the aqueous ink composition of the present invention uses a continuous ink jet printer, and is used in a case where the ink is recirculated at a relatively long time interval or used intermittently by an on-demand ink jet printer. It does not cause changes in the physical properties.
Furthermore, the image recorded on the information transmission sheet having the ink receiving layer by the water-based ink composition of the present invention has various fastness properties such as water resistance, moisture resistance, ozone gas resistance, abrasion resistance, and light resistance, particularly The water resistance and ozone gas resistance are good, and for this reason, the long-term storage stability of photographic images is also excellent. Compared to conventional inks, it also has excellent color development properties such as saturation, brightness, and print density on plain paper, color rendering properties, especially sensor compatibility in the near-infrared light region, and high color development properties. Yes.
Thus, the water-based ink composition of the present invention is extremely useful for various recording ink applications, particularly for ink jet recording ink applications.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by the following example.
In the text, “parts” and “%” are based on mass unless otherwise specified.
In the following formulas, acidic functional groups such as sulfo and carboxy are represented in the form of free acid.

[Preparation of carbon black dispersion]
By following the method described in Example 1 of Japanese Patent No. 3372163, a carbon black (# 45, Mitsubishi Chemical Corporation) dispersion was obtained.
However, in the final concentration step, concentration was performed to a pigment concentration of 10%.
[Example 1]
The compound of the following formula (3) as the component (A), the carbon black dispersion obtained above as the component (B), and other components are mixed at the composition ratio shown in Table 4 below, and the solid content is After stirring for approximately 1 hour until dissolution, a black ink composition for testing was prepared by filtering through a 0.80 μm membrane filter (trade name, cellulose acetate filter paper, manufactured by Advantech).
In addition, the compound of following formula (3) is the compound (21) described in International Publication No. 2006/051850, and was obtained by following the described method.
In the table, Surfactol ^RTM 440 manufactured by Nissin Chemical Co., Ltd. was used as the surfactant, and Proxel GXL (S) manufactured by Arch Chemicals was used as the preservative.

[Example 2]
A black ink composition for testing was prepared in the same manner as in Example 1 except that the components (A) and (B) and sodium hydroxide + ion exchanged water were changed to the number of parts in Example 2 in Table 4.
[Comparative Example 1]
As a black ink composition to be compared, C.I. I. A black ink composition for test was prepared in the same manner as in Example 2 except that Direct Black 19 was used.
[Comparative Example 2]
As a black ink composition to be compared, C.I. I. A test black ink was prepared in the same manner as in Example 2 except that Acid Black 2 was used.

[(B) Inkjet recording]
Using the respective ink compositions obtained in Examples 1 and 2 and Comparative Examples 1 and 2, inkjet recording was performed on the following printing paper using an inkjet printer (trade name: EPSON PX-105).
Plain paper 1: Product name Multipurpose manufactured by Hured Packard
Plain paper 2: Canon Inc. Brand name PB PAPER
At the time of printing, as a test piece for hue evaluation, the gradation of the reflection density is 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, and 10%. An image pattern was prepared so that a dark black to light black gradation recorded matter was obtained, and this was used as a test piece, and the following evaluation test was performed. In addition, as a test piece for evaluating moisture resistance, a lattice-like image pattern having a reflection density of 100% and 0% is prepared, black and white lattice-like recorded matter is obtained, and the following evaluation test is performed using this as a test piece. Carried out. Since the gray scale mode is used in any printing, yellow, cyan and magenta recording liquids other than the black recording liquid are not used in combination.

［耐水性評価］
実施例１、２、比較例１及び２のインクを用いて得られた各記録画像は、印刷後２４時間自然乾燥した後、水をスポイドで１滴滴下し、１時間自然乾燥した。試験終了後、目視にて上記の試験片を確認し、以下の基準で評価を行った。得られる評価としては、滲みが少ないものが耐水性良好であることを示し、優れている。結果を下記表６に示す。
○：有色格子を確認できる
×：有色格子が滲んで確認できない

[(C) Evaluation]
Regarding the recorded image by the aqueous ink composition of the present invention, the density change of the recorded image was measured using a colorimeter manufactured by GRETAG-MACBETH, trade name: SpectroEye. When measuring colors, all were performed under the conditions of D65 as the light source, DIN NB as the density reference, and a viewing angle of 2 °.
[Color development evaluation]
Each recorded image obtained using the inks of Examples 1 and 2 and Comparative Examples 1 and 2 was naturally dried for 24 hours after printing, and then measured using the above colorimeter. The measurement results of the optical density measurement value (OD) are shown in Table 5 below.

[Water resistance evaluation]
Each recorded image obtained using the inks of Examples 1 and 2 and Comparative Examples 1 and 2 was naturally dried for 24 hours after printing, and then one drop of water was dropped with a dropper, and then naturally dried for 1 hour. After completion of the test, the above test piece was visually confirmed and evaluated according to the following criteria. As the evaluation obtained, a sample with less bleeding shows excellent water resistance and is excellent. The results are shown in Table 6 below.
○: Colored grid can be confirmed ×: Colored grid is blurred and cannot be confirmed

From the results of Table 5, it was confirmed that Examples 1 and 2 both showed better results than Comparative Examples 1 and 2 in terms of color developability. Further, from the results of Table 6, it was confirmed that excellent water resistance was maintained.
As described above, the ink composition of the present invention can realize excellent color developability that has never been achieved while maintaining excellent water resistance.

The ink composition of the present invention is very excellent in color developability. In addition, the printing density is very high, the saturation is low, it has a high-quality black hue, and it has excellent water resistance, so it is suitable for black ink for various recordings such as writing utensils, especially inkjet recording. Used.

Claims (16)

(A) An ink composition containing a pigment represented by the following formula (1) and (B) carbon black.

[In Formula (1),
R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a phospho group; a nitro group; (C1-C4) alkyl group; (C1-C4) alkoxy group; hydroxy group, or (C1-C4) alkyl group substituted with (C1-C4) alkoxy group; hydroxy group, (C1-C4) alkoxy group, (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a sulfo group and a carboxy group; an acyl group; an N-alkylaminosulfonyl group; an N-phenylaminosulfonyl group; a sulfo group; N-alkylaminosulfuryl substituted with at least one group selected from the group consisting of a carboxy group and a hydroxy group An alkylsulfonyl group; an alkylsulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group; an acylamino group; an alkylsulfonylamino group; a phenylsulfonylamino group; Or a phenylsulfonylamino group substituted with at least one group selected from the group consisting of halogen atoms, (C1-C4) alkyl groups, and nitro groups;
R ³ and R ⁴ are each independently substituted with a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; a (C1-C4) alkyl group; a hydroxy group, or a (C1-C4) alkoxy group. (C1-C4) alkyl group; (C1-C4) alkoxy group; substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group, and carboxy group (C1-C4) alkoxy group; (C1-C4) alkylthio group; (C1-C4) alkylthio group substituted by sulfo group or carboxy group; acylamino group; alkylsulfonylamino group; phenylsulfonylamino group; At least one selected from the group consisting of an atom, a (C1-C4) alkyl group, and a nitro group; And; in substituted phenylsulfonylamino group
n represents 0 or 1, respectively. ] 2. The ink composition according to claim 1, wherein the carbon black is a self-dispersing carbon black having at least one hydrophilic group on a surface thereof directly or via another atomic group. In equation (1),
The ink composition according to claim 1, wherein 5 or more of R ^{1 to} R ⁷ are water-soluble substituents. In equation (1),
The ink composition according to any one of claims 1 to 3, wherein three or more of R ^{1 to} R ⁷ are a sulfo group or a carboxy group. In equation (1),
R ¹ and R ² are each independently a hydrogen atom; a sulfo group; a carboxy group; or a hydroxy group;
R ³ and R ⁴ are each independently a hydrogen atom; a halogen atom; a carboxy group; a sulfo group; a (C1-C4) alkoxy group substituted with a sulfo group or a carboxy group; or a sulfo group or a carboxy group. A substituted (C1-C4) alkylthio group;
R ^{5 to} R ⁷ are each independently a hydrogen atom; a halogen atom; a sulfo group; a carboxy group; a hydroxy group; or a (C1-C4) alkoxy group;
n is 1,
The ink composition according to any one of claims 1 to 4. In the formula (1),
R ¹ is a carboxy group or a sulfo group,
R ² is a hydrogen atom,
R ³ is a sulfo group,
R ⁴ is a hydrogen atom,
R ⁵ is a hydrogen atom, a carboxy group or a sulfo group,
R ⁶ is a carboxy group or a sulfo group,
R ⁷ is a hydrogen atom,
The ink composition according to any one of claims 1 to 5, wherein n is 1. The carbon black has at least one carboxy group [—COOM (wherein M represents a hydrogen atom, alkali metal, ammonium, or organic ammonium)] directly or via another atomic group on the surface. The ink composition according to claim 1, which is self-dispersing carbon black. The ink composition according to any one of Claims 1 to 7, wherein the total content of the component (A) and the component (B) is 3% by mass or more and less than 15% by mass. The ink composition according to any one of claims 1 to 8, wherein the content of carbon black is 50% by mass or more and less than 90% by mass in the total amount of the pigment content in the ink composition. The ink composition according to any one of claims 1 to 9, further comprising (C) a water-soluble organic solvent. The ink composition according to any one of claims 1 to 10, which is for inkjet recording. An ink jet recording method using the ink composition according to any one of claims 1 to 11 as ink, ejecting ink droplets of the ink in accordance with a recording signal, and depositing the ink on a recording material. The inkjet recording method according to claim 12, wherein the recording material is an information transmission sheet. 14. The ink jet recording method according to claim 12, wherein the information transmission sheet is a sheet having a paper or an ink receiving layer containing a porous white inorganic substance. A colored body colored by the ink jet recording method according to claim 12. An ink jet printer loaded with a container containing the ink composition according to claim 1.