JP2004307844A - Pigment mixture, ink, ink set and ink jet recording method using ink or ink set, pigmented product and process for preparation thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment mixture with favorable tint as a cyan ink, excellent light fastness, ozone resistance and moisture resistance, and suitable for ink jet recording. <P>SOLUTION: The pigment mixture is shown by formula (1) wherein R<SB>2</SB>, R<SB>3</SB>, R<SB>6</SB>, R<SB>7</SB>, R<SB>10</SB>, R<SB>11</SB>, R<SB>14</SB>and R<SB>15</SB>each independently represents an unsubstituted sulfamoyl group (-SO<SB>2</SB>NH<SB>2</SB>), sulfone group (-SO<SB>3</SB>M) or hydrogen atom with a proviso at least one of R<SB>2</SB>, R<SB>3</SB>, R<SB>6</SB>, R<SB>7</SB>, R<SB>10</SB>, R<SB>11</SB>, R<SB>14</SB>and R<SB>15</SB>represents an unsubstituted sulfamoyl group, R<SB>1</SB>, R<SB>4</SB>, R<SB>5</SB>, R<SB>8</SB>, R<SB>9</SB>, R<SB>12</SB>, R<SB>13</SB>and R<SB>16</SB>each represent hydrogen atom, M represents a proton, an alkali metal ion, an alkaline earth metal ion, an onium ion of an organic amine or an ammonium ion. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a dye mixture, an ink, an ink set, an inkjet recording method using the ink or the ink set, a colored body, and a manufacturing method.

In recent years, as an image recording material, especially a material for forming a color image has been mainly used. Specifically, an ink jet recording material, a thermal transfer type image recording material, a recording material using an electrophotographic method, a transfer type halogen, Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. Color filters are used in LCDs and PDPs for displays, and in electronic parts such as CCDs for photographing equipment. In these color image recording materials and color filters, in order to reproduce or record a full-color image, dyes and pigments of three primary colors by an additive color mixing method or a subtractive color mixing method are used, but a preferable color reproduction range can be realized. The fact is that there is no dye that has absorption characteristics and can withstand various use conditions, and improvement is strongly desired.

The ink jet recording method is rapidly spreading and further developing because of its low material cost, high-speed recording, low noise at the time of recording, and easy color recording. Ink jet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in response to an image information signal. , A method in which bubbles are generated in ink by heat to discharge droplets, a method using ultrasonic waves, and a method in which droplets are sucked and discharged by electrostatic force. Examples of inks suitable for inkjet recording include aqueous inks, oil-based inks, and solid (fused) inks.

For dyes used in inks suitable for such ink jet recording, the solubility or dispersibility in a solvent is good, high density recording is possible, the hue is good, light, heat, Strong against environmental active gases (oxidizing gases such as NOx and ozone, as well as SOx), excellent in durability against water and chemicals, good in fixability to recording materials, and resistant to bleeding. It is required that the ink be excellent in storage stability, not toxic, and be available at low cost. In particular, cyan dyes having a good cyan hue and excellent light resistance (durability to light), ozone resistance (durability to ozone gas) and moisture resistance (durability under high humidity) are strongly desired. .

Representative skeletons of water-soluble cyan dyes used in inks suitable for ink-jet recording are phthalocyanine-based and triphenylmethane-based. The most widely reported and used representative phthalocyanine dyes include phthalocyanine derivatives classified into the following A to H.

A: Phthalocyanine dyes such as Direct Blue 86, Direct Blue 87, Direct Blue 199, Acid Blue 249 or Reactive Blue 71 [for example, a mixture of Cu-Pc- (SO ₃ Na) m = 1 to m = 1 to 4]

B: phthalocyanine-based dyes described in Patent Documents 1 to 3 and the like [for _{example, Cu-Pc- (SO 3 Na} ) m (SO 2 NH 2) n: a mixture of m + n = 1 to 4]

C: phthalocyanine-based coloring matter described in Patent Literature 4 and the like [for _{example, Cu-Pc- (CO 2 H} ) m (CONR 1 R 2) n: m + n = 0~4 number]

D: phthalocyanine-based coloring matter described in Patent Literature 5 and the like [for _{example, Cu-Pc- (SO 3 H} ) m (SO 2 NR 1 R 2) n: m + n = 0~4 number, and, m ≠ 0]

E: phthalocyanine-based coloring matter described in Patent Literature 6 and the like [for _{example, Cu-Pc- (SO 3 H} ) l (SO 2 NH 2) m (SO 2 NR 1 R 2) n: l + m + n = 0~4 number]

F: Phthalocyanine dyes described in Patent Document 7 and the like [for example, Cu-Pc- (SO ₂ NR ₁ R ₂ ) n: n = 1 to 5]

G: Phthalocyanine-based dyes described in Patent Documents 8 and 9 [phthalocyanine-based dye in which substitution position of substituent is controlled, phthalocyanine-based dye having substitution type introduced at β-position]

H: Phthalocyanine dye having a pyridine ring described in Patent Document 10 and the like

A phthalocyanine dye represented by Direct Blue 86 or Direct Blue 199, which is widely used at present, is characterized by having superior light fastness compared to generally known magenta dyes and yellow dyes. The phthalocyanine dye has a greenish hue under acidic conditions, and is not preferable as a cyan ink. Therefore, when these dyes are used as cyan ink, it is preferable to use them under neutral to alkaline conditions. However, even if the ink is neutral to alkaline, the hue of the printed matter may significantly change when the recording material used is acidic paper.

Further, oxidizing gases such as nitrogen oxide gas and ozone, which are often taken up as an environmental problem in recent years, cause discoloration and decoloration to a greenish taste, and at the same time decrease the print density.

On the other hand, the triphenylmethane type has good hue, but is very poor in light fastness, ozone fastness and moisture fastness.

In the future, when the field of use is expanded and widely used for exhibitions such as advertisements, it is often exposed to light or active gas in the environment. Inexpensive dyes and inks that are resistant to environmental active gases (oxidizing gases such as NOx and ozone, as well as SOx, etc.) and that are inexpensive are increasingly desired. However, it is difficult to develop a cyan dye (for example, a phthalocyanine dye) and a cyan ink satisfying these requirements at a high level. So far, phthalocyanine dyes imparted with active gas resistance have been disclosed in Patent Documents 3, 8 to 11, and the like, but satisfy all qualities such as hue, light fastness, ozone fastness, and moisture fastness. Inexpensive cyan dyes and cyan inks have not yet been obtained. Therefore, the market has not yet been sufficiently satisfied.

JP-A-62-190273 JP-A-7-138511 JP-A-2002-105349 JP-A-5-17085 JP-A-10-140063 Japanese Patent Publication No. Hei 11-515048 JP-A-59-22967 JP-A-2000-303909 JP-A-2002-249677 JP 2003-34758 A JP-A-2002-80762

An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a dye having a good hue as a cyan ink and having excellent light fastness, ozone fastness and moisture fastness, an ink suitable for inkjet, and an inkjet recording method.

〔式中、Ｒ₂、Ｒ₃、Ｒ₆、Ｒ₇、Ｒ₁₀、Ｒ₁₁、Ｒ₁₄、Ｒ₁₅は各々独立して無置換スルファモイル基（−ＳＯ₂ＮＨ₂）、スルホン基（−ＳＯ₃Ｍ）又は水素原子を表わす。但し、Ｒ₂、Ｒ₃、Ｒ₆、Ｒ₇、Ｒ₁₀、Ｒ₁₁、Ｒ₁₄、Ｒ₁₅のうち少なくとも１つは無置換スルファモイル基である。又、Ｒ₁、Ｒ₄、Ｒ₅、Ｒ₈、Ｒ₉、Ｒ₁₂、Ｒ₁₃、Ｒ₁₆は水素原子を、Ｍはプロトン、アルカリ金属イオン、アルカリ土類金属イオン、有機アミンのオニウムイオンまたはアンモニウムイオンをそれぞれ示す。〕
（２）Ｒ₂とＲ₃、Ｒ₆とＲ₇、Ｒ₁₀とＲ₁₁、Ｒ₁₄とＲ₁₅の各組み合わせにおいて、それぞれの一方が水素原子であり、もう一方が無置換スルファモイル基（−ＳＯ₂ＮＨ₂）又はスルホン基（−ＳＯ₃Ｍ）であり、かつＲ₂、Ｒ₃、Ｒ₆、Ｒ₇、Ｒ₁₀、Ｒ₁₁、Ｒ₁₄、Ｒ₁₅のうち、少なくとも１つは無置換スルファモイル基である（１）に記載の色素の混合物、
（３）下記式（２）で表される化合物又はその塩に塩素化剤を反応させ、スルホン基をクロロスルホン基に置換し、アミド化剤を反応させて得られたものである式（１）で表わされる（１）又は（２）に記載の色素の混合物、

〔式中、Ｍはプロトン、アルカリ金属イオン、アルカリ土類金属イオン、有機アミンのオニウムイオンまたはアンモニウムイオンを示す。ａ、ｂ、ｃ、ｄは０又は１で、その和は１〜４の整数である。〕
（４）４−スルホフタル酸誘導体又は、４−スルホフタル酸誘導体と（無水）フタル酸誘導体を銅化合物の存在下に反応させることにより得られる化合物またはその塩に塩素化剤を反応させ、スルホン酸基をクロロスルホン化した後、アミド化剤を反応させて得られた色素の混合物、
（５）色素成分として（１）から（４）のいずれか一項に記載の色素混合物を含むことを特徴とするインク、
（６）水溶性有機溶剤を含有する（５）に記載のインク、
（７）インクジェット記録用である（５）又は（６）に記載のインク、
（８）色素濃度の異なる２種以上のシアンインクを用いるインクジェットプリンタにおいて、少なくとも１種は（５）から（７）のいずれか一項に記載のインクを用いることを特徴とするインクセット、
（９）色素濃度の異なる２種以上のシアンインクを用いるインクジェットプリンタにおいて、色素濃度の最も低いインクに（５）から（７）のいずれか一項に記載のインクを用いることを特徴とするインクセット、
（１０）インク滴を記録信号に応じて吐出させて被記録材に記録を行うインクジェット記録方法において、（５）から（９）のいずれか一項に記載のインク又はインクセットを用いることを特徴とするインクジェット記録方法、
（１１）被記録材が情報伝達用シートである（１０）に記載のインクジェット記録方法、
（１２）情報伝達用シートが表面処理されたシートであって、支持体上に白色無機顔料粒子を含有するインク受像層を有するシートである（１１）に記載のインクジェット記録方法、
（１３）（５）から（９）のいずれか一項に記載のインク又はインクセットを含有する容器、
（１４）（１３）に記載の容器を有するインクジェットプリンタ、
（１５）（５）から（９）のいずれか一項に記載のインク又はインクセットを用いて着色された着色体、
（１６）４−スルホフタル酸誘導体又は、４−スルホフタル酸誘導体と（無水）フタル酸誘導体を銅化合物の存在下に反応させることにより得られる化合物またはその塩に塩素化剤を反応させ、スルホン酸基をクロロスルホン化した後、アミド化剤を反応させて得られた色素の混合物の製造方法、
に関する。 The present inventors have studied in detail phthalocyanine dyes having high hue and light resistance and high ozone resistance, by using a compound using a mixture of specific phthalocyanine dyes as a dye for ink, The inventors have found that the above problems can be solved, and have completed the present invention. More specifically, the present invention relates to a metal phthalocyanine dye represented by the following formula (1) having both a sulfo group and a sulfamoyl group at a specific substitution position (β-position: see below). The present invention was found to have a dye, and was found to be excellent in light resistance (durability to light), moisture resistance (durability under high humidity) and ozone resistance (durability to ozone gas), and completed the present invention. Hereinafter, the present invention will be described in detail. That is, the present invention
(1) a mixture of dyes represented by the following formula (1),

[Wherein, R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ each independently represent an unsubstituted sulfamoyl group (—SO ₂ NH ₂ ), a sulfone group (—SO ₃ M) or a hydrogen atom. However, at least one of R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ is an unsubstituted sulfamoyl group. R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ , and R ₁₆ represent a hydrogen atom, M represents a proton, an alkali metal ion, an alkaline earth metal ion, an onium ion of an organic amine or Ammonium ions are shown respectively. ]
(2) In each combination of R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , and R ₁₄ and R ₁₅ , one of them is a hydrogen atom and the other is an unsubstituted sulfamoyl group (—SO ₂ NH ₂ ) or a sulfone group (—SO ₃ M), and at least one of R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ is unsubstituted sulfamoyl. A mixture of the dyes according to (1), which is a group;
(3) A compound represented by the following formula (1) obtained by reacting a compound represented by the following formula (2) or a salt thereof with a chlorinating agent, replacing a sulfone group with a chlorosulfone group, and reacting with an amidating agent. A mixture of the dyes according to (1) or (2),

[In the formula, M represents a proton, an alkali metal ion, an alkaline earth metal ion, an onium ion or an ammonium ion of an organic amine. a, b, c, and d are 0 or 1, and the sum is an integer of 1 to 4. ]
(4) A chlorinating agent is reacted with a compound or a salt thereof obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a copper compound to form a sulfonic acid group. After chlorosulfonation, a mixture of dyes obtained by reacting an amidating agent,
(5) an ink comprising the dye mixture according to any one of (1) to (4) as a dye component,
(6) the ink according to (5), containing a water-soluble organic solvent;
(7) The ink according to (5) or (6), which is for inkjet recording.
(8) In an ink-jet printer using two or more kinds of cyan inks having different dye concentrations, at least one kind uses the ink according to any one of (5) to (7),
(9) In an ink jet printer using two or more types of cyan inks having different dye concentrations, the ink according to any one of (5) to (7) is used as the ink having the lowest dye concentration. set,
(10) In an ink jet recording method for performing recording on a recording material by discharging ink droplets according to a recording signal, the ink or the ink set according to any one of (5) to (9) is used. Inkjet recording method,
(11) The inkjet recording method according to (10), wherein the recording material is an information transmission sheet.
(12) The ink-jet recording method according to (11), wherein the information transmission sheet is a surface-treated sheet, and the sheet has an ink image-receiving layer containing white inorganic pigment particles on a support.
(13) A container containing the ink or the ink set according to any one of (5) to (9),
(14) An inkjet printer having the container according to (13),
(15) a colored body colored using the ink or the ink set according to any one of (5) to (9),
(16) A chlorinating agent is reacted with a compound or a salt thereof obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a copper compound, to form a sulfonic acid group After chlorosulfonation, a method for producing a mixture of dyes obtained by reacting an amidating agent,
About.

The ink using the dye mixture of the present invention has an excellent hue as a cyan ink and is excellent in light fastness, ozone fastness and moisture fastness. Further, there is no crystal precipitation, physical property change, color change and the like after long-term storage, and the storage stability is good. Further, when used together with other magenta ink and yellow ink, it is possible to color tone in a wide visible region. Further, the dye mixture of the present invention can be produced at low cost without using a particularly difficult method. Therefore, a cyan ink using the dye mixture of the present invention is extremely useful as an ink for inkjet recording.

  Hereinafter, the present invention will be described in detail. The mixture of the dye represented by the formula (1) according to the present invention can be used as a compound obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a copper compound. A chlorinating agent is reacted to convert a sulfonic acid group to a chlorosulfone group, and then an amidating agent is reacted, thereby introducing a sulfonic acid group and a sulfamoyl group at a specific substitution position (β-position) of the phthalocyanine ring. can get. Printed matter using the dye has extremely excellent resistance to ozone gas.

The cyan ink of the present invention contains a mixture of the dyes represented by the formula (1), and is mainly used as an ink for inkjet recording as a cyan color.

Generally, a phthalocyanine derivative may inevitably include, at the time of its synthesis, substitution position isomers of substituents R _{1 to} R ₁₆ in the following formula (1), and these substitution position isomers are the same without being distinguished from each other. Often regarded as derivatives.

Phthalocyanine derivatives having different substitution positions are defined by classifying them into the following three types. Hereinafter, in the present specification, when describing phthalocyanine derivatives having different substitution positions, (1) β-position-substituted type, (2) α- And (3) α, β-position mixed substitution type.

(1) β-position-substituted type: (a phthalocyanine compound having a substituent at any one or more of the 2-, 3-, 6-, 7-, 10-, 11-, 14-, and 15-positions)
(2) α-position-substituted type: (a phthalocyanine compound having a substituent at any one or more of positions 1, 4, 5, 8, 9, 12, 13, and 16)
(3) α, β-position mixed substitution type: (phthalocyanine compound having a substituent at any position at 1 to 16 positions)
The mixture of the phthalocyanine dyes represented by the formula (1) of the present invention belongs to the above β-substituted type.

The compound represented by the formula (2) or a salt thereof is prepared according to the methods described in (0010) to (0011) and (0029) to (0030) of Patent Document 8, and for example, the phthalocyanine dye of the present invention comprises 4- A chlorinating agent is reacted with a compound (β-position-substituted sulfophthalocyanine) obtained by reacting sulfophthalic acid derivatives with each other or a 4-sulfophthalic acid derivative and a (phthalic anhydride) phthalic acid derivative in the presence of a metal compound; It is obtained by converting a sulfonic acid group into a chlorosulfone group and then reacting with an amidating agent. By changing the molar ratio of the reaction between 4-sulfophthalic acid and (phthalic anhydride), the number of sulfone groups, that is, the number of ad can be adjusted.
The 4-sulfophthalic acid derivative used as a raw material generally contains about 15 to 25% by weight of an impurity sulfonated at the 3-position as an impurity, and the α-substituted product derived therefrom is mixed into the target phthalocyanine dye. In order to further enhance the effects of the present invention (especially in order to obtain an ink having high ozone resistance), it is preferable to use a raw material having a low content of impurities sulfonated at the 3-position.
The reaction temperature is usually 150 to 290 ° C, preferably 170 to 270 ° C at normal pressure. The reaction time varies depending on the reaction temperature, but is usually 1 to 8 hours.
In the target phthalocyanine dye, a chlorosulfone group partially decomposed during the reaction is mixed into the reaction product, but this does not cause any problem. The obtained dye is represented by the following formula (9), and it is considered that the β-substituted substance is a main component, that is, at least 60%, preferably 70% or more, and more preferably 75% or more.

(In the formula (9), the sum of l and m is 2 or more and 4 or less, and the values of l and m indicate average values in the mixture.)

The mixture of the dye represented by the formula (1) according to the present invention is obtained by substituting a part of the sulfone group with a chlorosulfone group with chlorosulfonic acid or the like using the compound of the formula (2) or a salt thereof as a raw material. If necessary, a chlorinating agent is added, and further substituted with chlorosulfone groups.

Examples of the chlorinating agent used in the above reaction include, but are not limited to, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, chlorosulfonic acid and the like.

Next, the thus obtained copper phthalocyanine chlorosulfonate is reacted with an amidating agent to obtain a mixture of the dyes represented by the formula (1). The amount of the amidating agent to be reacted is usually 1.5 times or more the theoretical value, preferably 2.0 times or more, more preferably 2.5 times or more in terms of molar ratio with the raw material. Examples of the amidating agent used in the reaction include, but are not limited to, ammonium salts such as ammonium chloride and ammonium sulfate, preferably ammonium salts of inorganic acids, urea, aqueous ammonia, and ammonia gas.

For example, when a compound of the formula (2) or a salt thereof is substituted with a chlorosulfone group in a chlorosulfonic acid for a sulfone group, the amount of the chlorosulfonic acid used is a mass ratio to the compound of the formula (2) or a salt thereof. The amount is usually 3 to 20 times, preferably 5 to 10 times. The reaction temperature is usually from 60 to 140 ° C. The reaction time varies depending on the reaction temperature, but is usually 30 minutes to 10 hours, preferably 1 to 6 hours. After completion of the reaction, the reaction solution is poured into ice water and filtered to obtain a wet cake of a chlorosulfonate of the compound of the formula (2) or a salt thereof. The thus obtained chlorosulfonated compound of the formula (2) has a substituent at the β-position, but has 1 to 4 chlorosulfone groups, and thus has been chlorosulfonated. The resulting compound exists as a dye mixture containing the isomers.

For example, when a compound of the formula (2) or a salt thereof is substituted with a chlorosulfone group in a chlorosulfonic acid for a sulfone group, the amount of the chlorosulfonic acid used is a mass ratio to the compound of the formula (2) or a salt thereof The amount is usually 3 to 20 times, preferably 5 to 10 times. The reaction temperature is usually from 60 to 140 ° C. The reaction time varies depending on the reaction temperature, but is usually 30 minutes to 10 hours, preferably 1 to 6 hours. After completion of the reaction, the reaction solution is poured into ice water and filtered to obtain a wet cake of a chlorosulfonate of the compound of the formula (2) or a salt thereof. The thus obtained chlorosulfonated compound of the formula (2) has a substituent at the β-position, but has 1 to 4 chlorosulfone groups, and thus has been chlorosulfonated. The resulting compound exists as a dye mixture containing the isomers.

To use a chlorinating agent in combination, for example, the compound of the formula (2) or a salt thereof is replaced with a chlorosulfone group in a chlorosulfonic acid. The amount of chlorosulfonic acid to be used is usually 3 to 20 times, preferably 5 to 10 times, the mass of the compound of the formula (2) or a salt thereof. The reaction temperature is usually from 60 to 140 ° C. The reaction time varies depending on the reaction temperature, but is usually 30 minutes to 10 hours, preferably 1 to 6 hours. Thereafter, a chlorinating agent is added to further increase the degree of chlorosulfonation. The amount of the chlorinating agent to be used is generally 1 to 100 times, preferably 3 to 80 times, the molar ratio of the compound of the formula (2) or a salt thereof. The reaction temperature is usually from 60 to 140 ° C. The reaction time varies depending on the reaction temperature, but is usually 30 minutes to 10 hours, preferably 1 to 6 hours. After completion of the reaction, the reaction solution is poured into ice water and filtered to obtain a wet cake of a chlorosulfonate of the compound of the formula (2) or a salt thereof. The thus obtained chlorosulfonated compound of the formula (2) has a substituent at the β-position, but has 1 to 4 chlorosulfone groups, and thus has been chlorosulfonated. The resulting compound exists as a dye mixture containing the isomers.
In the synthesis of the compound of the formula (1), an impurity in which a chloro group is partially introduced into the phthalocyanine ring is generated in the dye mixture of the formula (1) by a reaction such as substitution with a chlorosulfone group. However, such impurities do not hinder the effects of the present invention.

Further, in the mixture of the dyes represented by the formula (1) satisfying the above conditions, CuPc (copper phthalocyanine ring) is partially dimerized via L (a divalent linking group) (for example, (CuPc-L-CuPc) or an impurity in the form of a trimer may be generated and mixed into the reaction product. In this case, a plurality of L may be the same or different. Good.

The divalent linking group represented by L includes —SO ₂ — (sulfonyl group), —SO ₂ —NH—SO ₂ — and the like, and may be a group formed by combining these.

The dye mixture of the present invention thus obtained can be separated by filtration or the like after acid precipitation or salting out. The salting out is preferably carried out, for example, in the range of acidic to alkaline, preferably in the range of about pH 4 to 11. The temperature at the time of salting out is not particularly limited, but it is generally preferable to heat to 40 to 80 ° C, preferably 50 to 70 ° C, and then add salt and the like for salting out.

The dye mixture of the present invention synthesized by the above method is represented by the above formula (1), and R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ are each independently an unsubstituted sulfamoyl group (-SO ₂ NH _2), represents a sulfone group (-SO ₃ M) or a hydrogen _{atom, R 2, R 3, R} 6, R 7, R 10, R 11, R 14, R of _15, at least one unsubstituted sulfamoyl _{group, R 1, R 4, R} 5, R 8, R 9, R 12, R 13, R 16 is a β- substituted copper phthalocyanine which is a hydrogen atom It is a mixture.
In the combination of R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , and R ₁₄ and R ₁₅ , one is preferably a hydrogen atom and the other is preferably an unsubstituted sulfamoyl group (—SO ₂ NH a ₂₎ or a sulfone group (-SO ₃ M), and _{R 2, R 3, R 6} , R 7, R 10, R 11, among of R _14, R _15, at least one unsubstituted sulfamoyl group is there. SO ₃ M of the sulfone group of the formula (1) is obtained in the form of a free acid or a salt thereof. In order to obtain a free acid, for example, acid precipitation may be performed. In addition, salt formation is carried out by salting out, or when a desired salt cannot be obtained by salting out, for example, a usual salt exchange method in which a desired organic or inorganic base is added to a free acid is used. Just fine.

In the mixture of the dyes of the formulas (1) and (2), M represents a proton, an alkali metal ion, an alkaline earth metal ion, an onium ion or an ammonium ion of an organic amine. Examples of the alkali metal in the alkali metal ion of M include sodium, potassium, lithium and the like. Examples of the alkaline earth metal in the alkaline earth metal ion include calcium and magnesium. As the organic amine, examples of the alkylamine include lower alkylamines having 1 to 4 carbon atoms such as methylamine and ethylamine. Examples of the alkanolamine include mono, di or tri (lower alkanol having 1 to 4 carbon atoms) amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine. Preferred M is, for example, an alkali metal ion such as proton, ammonium ion, sodium ion, potassium ion and lithium ion; alkanolamine such as monoethanolamine, diethanolamine, trienolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine. Preferable examples include an onium ion of mono, di or tri (lower alkanol having 1 to 4 carbon atoms) amine. However, the form of the ions is not limited to those described above.

The cyan ink of the present invention contains a mixture of the dyes of the formula (1) produced by the above method, and is prepared using water as a medium. When this ink is used as an ink for ink jet recording, the dye mixture is used. It is preferable to use those having a small content of anions such as Cl ^- and SO ₄ ^2- contained in the dye mixture. The standard of the content is 5 mass% as the total content of Cl ^- and SO ₄ ^{2- in} the dye mixture. %, Preferably 3% by mass or less, more preferably 1% by mass or less, and 1% by mass or less in the ink. Cl ^- and SO ₄ in the production of dye mixture of ² less present invention, stirring the dried product or a wet cake of the dye mixtures of the usual methods or the present invention using a reverse osmosis membrane for example an alcohol, and a mixed solvent of water Then, desalting may be performed by a method such as filtration and drying. The alcohol used is a lower alcohol having 1 to 4 carbon atoms, preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol, ethanol or 2-propanol. Further, at the time of desalting treatment with alcohol, a method of heating to near the boiling point of the alcohol to be used, followed by cooling and desalting may be employed. Cl ^- and SO ₄ content of ² is measured by an ion chromatography.

When the cyan ink of the present invention is used as an ink for ink jet recording, an ink having a low content of heavy metals (ions) such as zinc and iron, and metals (cations) such as calcium and silica contained in the dye mixture is used. (The dye mixture used in the present invention excludes copper because the dye contains copper.) The standard of the content is, for example, about 500 ppm or less for each of heavy metals (ions) such as zinc and iron and metals (cations) such as calcium and silica in a purified and dried product of the dye mixture. The contents of heavy metals (ions) and metals (cations) are measured by ion chromatography, atomic absorption, or ICP (Inductively Coupled Plasma) emission spectrometry.

The mixture of the dye of the formula (1) is contained in the ink of the present invention in an amount of 0.1 to 8% by mass, preferably 0.3 to 6% by mass. The low-concentration ink contains 0.1 to 2.5% by weight of the dye mixture of the present invention.

The ink of the present invention is prepared using water as a medium. The ink of the present invention contains 0.3 to 6% by mass of the mixture of the compound of the formula (1) or the salt thereof satisfying the above conditions and obtained as described above. If necessary, the ink of the present invention further contains a water-soluble organic solvent within a range that does not impair the effects of the present invention. The water-soluble organic solvent is used as a dye dissolving agent, an anti-drying agent (wetting agent), a viscosity adjusting agent, a penetration enhancer, a surface tension adjusting agent, an antifoaming agent, and the like. Other ink preparations include, for example, preservatives and fungicides, pH adjusters, chelating agents, rust inhibitors, ultraviolet absorbers, viscosity adjusters, dye dissolving agents, anti-fading agents, emulsion stabilizers, surface tension adjusters, Known additives such as an antifoaming agent, a dispersant, and a dispersion stabilizer are exemplified. The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation is preferably 0 to 20% by mass, preferably 0 to 15% by mass.

Examples of the water-soluble organic solvent that can be used in the present invention include C1-C4 alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol, and N, N-dimethyl. Carboxylic acid amides such as formamide or N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2- Heterocyclic ketones such as ON, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or cyclic ethers such as keto alcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2- or 1,3 -Propylene glycol, 1,2- Has (C2-C6) alkylene units such as 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, and polypropylene glycol. Monomers, oligomers or polyalkylene glycols or thioglycols, polyols (triols) such as glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or triethylene glycol Polyvalent such as ethylene glycol monomethyl ether or triethylene glycol monoethyl ether (C1 -C4) alkyl ethers of alcohol, gamma-butyrolactone or dimethyl sulfoxide and the like.

In the ink of the present invention, preferred as the water-soluble organic solvent are isopropanol, glycerin, mono, di or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, more preferably isopropanol, Glycerin, diethylene glycol and 2-pyrrolidone. These water-soluble organic solvents are used alone or as a mixture.

Examples of the antiseptic / antifungal agent include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloallyl sulfone-based, iodopropagyl-based, N-haloalkylthio-based, benzthiazole-based, nitritolyl-based, pyridine-based, and 8- Oxyquinoline type, benzothiazole type, isothiazoline type, dithiol type, pyridine acid type, nitropropane type, organic tin type, phenol type, quaternary ammonium salt type, triazine type, thiadiazine type, anilide type, adamantane type, dithiocarbamate type, Brominated indanone compounds, benzyl bromoacetate compounds, inorganic salt compounds and the like can be mentioned. Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine acid compound include sodium 2-pyridinethiol-1-oxide, and examples of the inorganic salt compound include sodium acetate anhydride. 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, -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 and the like. No. Other preservatives and fungicides include sodium sorbate sodium benzoate and the like (for example, Proxel GXL (S) and Proxel XL-2 (S) manufactured by Avecia).

As the pH adjuster, any substance can be used as long as it can control the pH of the ink in the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, alkanolamines such as diethanolamine and triethanolamine, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, and alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate Carbonates and the like.

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium uramildiacetate. Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

As the ultraviolet absorber, for example, a compound that absorbs ultraviolet light and emits fluorescence represented by a benzophenone-based compound, a benzotriazole-based compound, a cinnamic acid-based compound, a triazine-based compound, a stilbene-based compound, or a benzoxazole-based compound, so-called fluorescence Brighteners can also be used.

Examples of the viscosity modifier include a water-soluble polymer compound in addition to a water-soluble organic solvent, such as polyvinyl alcohol, a cellulose derivative, polyamine, and polyimine.

Examples of the dye dissolving agent include urea, ε-caprolactam, ethylene carbonate and the like.

The anti-fading agent is used for the purpose of improving the storability of an image. As an anti-fading agent, various organic and metal complex-based anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. Complexes and zinc complexes.

Examples of the surface tension modifier include surfactants, for example, anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants. Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acylmethyl taurine salts, alkyl sulfate polyoxyalkyl ethers Sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl alcohol sulfate, alkyl phenol phosphate, alkyl phosphate, alkyl allyl sulfonate, diethyl sulfosuccinate And diethylhexylsulfosuccinate dioctylsulfosuccinate. Examples of the cationic surfactant include a 2-vinylpyridine derivative and a poly-4-vinylpyridine derivative. Examples of the amphoteric surfactant include betaine lauryldimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amide propyldimethylaminoacetate betaine, polyoctyl polyaminoethylglycine, and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as alkyl ethers and polyoxyallylalkyl alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquis Esters such as oleate, polyoxyethylene monooleate and polyoxyethylene stearate, 2,4,7, Acetylene glycols such as -tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 465, Olfin STG, etc., manufactured by Nissin Chemical Co., Ltd.). These ink preparations are used alone or as a mixture. The surface tension of the ink of the present invention is usually 25 to 70 mN / m, and more preferably 25 to 60 mN / m. The viscosity of the ink of the present invention is preferably 30 mPa · s or less. It is more preferable to adjust the pressure to 20 mPa · s or less.

As the defoaming agent, a fluorine-based or silicone-based compound is used as needed.

In producing the ink of the present invention, there is no particular limitation on the order in which the respective chemicals are dissolved. In preparing the ink, the water used is preferably an ion-exchanged water or a water having a small amount of impurities such as distilled water. Further, if necessary, fine filtration may be performed using a membrane filter or the like to remove impurities. When used as an ink for an inkjet printer, it is preferable to perform fine filtration. The pore size of the filter for microfiltration is usually 1 micron to 0.1 micron, preferably 0.8 micron to 0.2 micron.

The ink of the present invention can be 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, it is also used as an ink set with magenta ink, yellow ink, and black ink. Further, in order to form a higher definition image, the ink set is used as an ink set in combination with light magenta ink, blue ink, green ink, orange ink, dark yellow ink, gray ink, and the like.

As a dye of the yellow ink that can be applied, a known and commonly used dye can be used. For example, an aryl or hetenylazo dye having a phenol, naphthol, aniline, heterocycle such as pyrazolone or pyridone, or an open-chain active methylene compound as a coupling component (hereinafter referred to as a coupler component); Azomethine dyes having open-chain active methylene compounds; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

As the dye of the magenta ink that can be applied, a known and commonly used dye can be used. For example, aryl or hetenylazo dyes having phenols, naphthols, anilines and the like as coupler components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupler components; for example, arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes, etc .; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., condensed polycycles such as quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., eg dioxazine dyes Dyes and the like can be mentioned.

Each of the above-mentioned dyes may exhibit each color of yellow, magenta and cyan only after a part of the chromophore dissociates, and in this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Or an organic cation such as a pyridinium or quaternary ammonium salt, or a polymer cation having these in a partial structure. Examples of applicable black dyes include disazo, trisazo, and tetraazo dyes, as well as carbon black dispersions.

The inks of the invention are suitable for use in printing, copying, marking, writing, drafting, stamping, or recording methods, especially ink jet printing.

In the ink jet recording method of the present invention, energy is supplied to the ink prepared by the above method, and known image receiving materials, that is, plain paper, resin-coated paper, ink jet dedicated paper, glossy paper, glossy film, and electrophotographic paper To form images on fibers, cloths (cellulose, nylon, wool, etc.), glass, metal, ceramics, leather and the like.

When forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting gloss, water resistance, or improving weather resistance. The timing of applying the polymer latex to the recording material may be before, after, or simultaneously with the application of the colorant. May be in the ink, or may be used as a liquid material of the polymer latex alone.

Hereinafter, a recording material (particularly, recording paper and recording film) used for performing inkjet printing using the ink of the present invention will be described. The support for recording paper and recording film is composed of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP and CGP, and waste paper pulp such as DIP as required. Known pigments, binders, sizing agents, fixing agents, cationic agents, additives such as paper strength enhancers are mixed, and those manufactured by various apparatuses such as Fourdrinier paper machines and circular net paper machines can be used. is there. In addition to these supports, any of synthetic paper and plastic film sheets may be used. 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 back coat layer as they are, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, and then providing an ink receiving layer and a back coat layer. Further, the support may be subjected to a flattening treatment using a calender such as a machine calender, a TG calender, and a soft calender. In the present invention, a paper and a plastic film laminated on both sides with a polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and a copolymer thereof) on both sides are more preferably used. It is preferable to add a white pigment (for example, titanium oxide, zinc oxide) or a coloring dye (for example, cobalt blue, ultramarine, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support may contain a pigment or 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 pigment, acrylic pigment, urea resin, and melamine resin. As the white pigment contained in the ink receiving layer, a porous inorganic pigment is preferable, and a synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, both silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include aqueous solutions of polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. And water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer. The ink receiving layer may contain a mordant, a water-proofing agent, a lightfastness improving agent, a surfactant, and other additives in addition to the pigment and the aqueous binder.

As the mordant added to the ink receiving layer, for example, a polymer mordant is used.

The water-proofing agent is effective for making the image water-resistant, and as such a water-proofing agent, a cationic resin is particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, and the like. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably from 1 to 15% by mass, more preferably from 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, and benzophenone-based and benzotriazole-based ultraviolet absorbers. Of these, zinc sulfate is preferred.

The surfactant functions as a coating aid, a release improver, a slipperiness improver, or an antistatic agent. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, ethylene tetrafluoride resin). Other additives added to the ink receiving layer include pigment dispersants, thickeners, defoamers, dyes, fluorescent brighteners, preservatives, pH adjusters, matting agents, hardeners, and the like. . The ink receiving layer may be a single layer or two layers.

A recording paper and a recording film may be provided with a back coat layer. Examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, and other white inorganic pigments Organic pigments such as styrene-based plastic pigments, acrylic-based plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.

Examples of the aqueous binder contained in the back coat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose. And water-soluble polymers such as hydroxyethylcellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

A polymer latex may be added to the constituent layers (including the back coat layer) of the inkjet recording paper and the recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

These recording papers and recording films are generally called inkjet special paper, glossy paper or glossy film, and include, for example, Pictorico (made by Asahi Glass Co., Ltd.), color BJ paper, high quality exclusive paper, color BJ photo film sheet , Super Photo Paper, Professional Photo Paper (all manufactured by Canon Inc.), Color Image Jet Paper (manufactured by Sharp Corporation), PM Photo Paper, Glossy Film for Super Fine (all manufactured by Epson Corporation), Picta It is commercially available as Fine (manufactured by Hitachi Maxell, Ltd.). In particular, the ink jet recording method using the ink of the present invention works particularly effectively on recording paper and recording films having an ink image receiving layer containing white inorganic pigment particles on a support as a recording material. Of course, it can also be used for plain paper.

The colored body using the ink of the present invention is obtained by printing the ink produced by the above method with an ink jet printer and coloring the ink.

In order to record on a recording material by the ink jet recording method of the present invention, for example, a container containing the above-mentioned ink may be set at a predetermined position of an ink jet printer, and recording may be performed on the recording material by a usual method. 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 ink according to the invention does not settle or separate during storage. Further, when the ink according to the present invention is used in ink-jet printing, the ejector (ink head) is not blocked. The inks according to the invention do not change their physical properties under constant recirculation for a relatively long period of time with continuous ink jet printers or even in intermittent use with on demand ink jet printers.

  The ink of the present invention has a clear cyan color, and can provide a recorded matter having particularly excellent ozone resistance, light resistance and water resistance. By using it as a set of shades of cyan ink, it can be used with other yellow, magenta, and other green, red, orange, blue, etc. In addition, it is possible to provide a color tone in a wide visible region, to obtain a recorded matter having excellent ozone resistance, light resistance and water resistance.

Hereinafter, the present invention will be described more specifically with reference to Examples. In the text, “part” and “%” are based on mass unless otherwise specified.

Example 1
(1) According to Example 1 described in Patent Document 8, a compound in which a, b, c, and d of the above formula (2) are 1 was obtained as follows.
40 parts of sulfolane was added to a four-necked flask equipped with a cooling tube, and the temperature was raised to 180 ° C. in 1 hour, and 40 parts of 4-sulfophthalic acid, 4.5 parts of ammonium chloride, 55 parts of urea, and 0 parts of ammonium molybdate were added. 0.5 parts and 6 parts of copper (II) chloride were added, and the mixture was stirred at the same temperature for 6 hours. After the reaction solution was cooled to 40 ° C., the target substance was filtered with Nutsche and washed with 400 parts of methanol. Subsequently, 300 parts of water is added to the obtained wet cake, the pH is adjusted to 10 with a 48% aqueous caustic solution, and the mixture is stirred at 80 ° C. for 1 hour. Then, a 35% hydrochloric acid aqueous solution was added to the mixture to adjust the pH to 3, while stirring, and 80 parts of common salt was gradually added thereto. The precipitated crystals were collected by filtration and washed with 150 parts of a 20% saline solution to obtain 90 parts of a wet cake. Subsequently, 210 parts of methanol was added and the mixture was stirred for 1 hour. The precipitated crystals were separated by filtration, washed with 300 parts of a 70% aqueous methanol solution and dried, and a, b, and b of the above formula (2) in which M is a sodium salt. 22.9 parts of the compound in which c and d were 1 were obtained as blue crystals. λmax: 629 nm (in an aqueous solution).
(2) 9.84 parts of the compound obtained in (1) was gradually charged at 70 ° C. or lower while stirring in 69.1 parts of chlorosulfonic acid, and reacted at 120 ° C. for 4 hours. After the reaction, the reaction solution obtained by cooling was poured into 300 parts of ice water to decompose the remaining chlorosulfonic acid. The precipitated crystals were filtered and washed with 67 parts of ice water to obtain 37.2 parts of a wet cake.
(3) To 130 parts of ice water, 37.2 parts (0.01 mol) of the wet cake obtained in (2) was added, and the mixture was stirred at 5 ° C. or lower for 30 minutes. While maintaining the temperature at 0 to 5 ° C, the pH was adjusted to 10 to 10.5 with aqueous ammonia. The reaction was carried out for 1 hour under the same conditions, and the reaction was carried out at 25 ° C. for 1 hour and at 60 ° C. for 1 hour while maintaining pH 9.5 to 10.0. 360 parts of a reaction mixture were obtained. The reaction mixture was adjusted to pH 7.0 with 10% hydrochloric acid at 60 ° C., and 72 parts of sodium chloride was gradually added. After stirring for 30 minutes, the precipitated crystals were separated by filtration to obtain 40.2 parts of a wet cake.
(4) While stirring in 200 parts of methanol, 40.2 parts of the wet cake of (3) was added and stirred for 1 hour. The crystals were separated by filtration and washed with 50 parts of methanol to obtain a wet cake. The wet cake was again added to 150 parts of methanol, and the obtained wet cake (18.5 parts) was dried to obtain 9.3 parts of a dye mixture. This dye mixture has a β-substituted substance of 75% or more, a λmax in water of 603.0 nm, Cl ⁻ : 0.1% or less, SO ₄ ²⁻ : 0.1% or less, Fe: 100 ppm or less, Zn: 100 ppm or less, Ca: 200 ppm or less.

Example 2
Chlorination was carried out in the same manner as in Example 1 in an amount of 46.0 parts of chlorosulfonic acid, and 36.0 parts of a wet cake of the dye mixture having a sulfamoylation rate lower than that of the dye mixture obtained in Example 1 was used. Obtained. This was reacted with ammonia water in the same manner as in Example 1 and purified to obtain 9.1 parts of a dried product (colorant mixture). This dye mixture has a β-substituted substance of 75% or more, a λmax in water of 605.5 nm, Cl ⁻ : 0.1% or less, SO ₄ ²⁻ : 0.1% or less, Fe: 100 ppm or less, Zn: 100 ppm or less, Ca: 200 ppm or less.

Example 3
Chlorination was carried out in the same manner as in Example 1 in the use amount of chlorosulfonic acid of 34.6 parts, and 36.6 parts of a wet cake of the dye mixture having a sulfamoylation rate lower than that of the dye mixture obtained in Example 2 was used. Obtained. This was reacted with ammonia water in the same manner as in Example 1 and purified to obtain 8.8 parts of a dried product (colorant mixture). This dye mixture has a β-substituted substance of 75% or more, a λmax in water of 611.0 nm, Cl ⁻ : 0.1% or less, SO ₄ ²⁻ : 0.1% or less, Fe: 100 ppm or less, Zn: 100 ppm or less, Ca: 200 ppm or less.

Example 4
(1) While stirring in 46.0 parts of chlorosulfonic acid at a temperature of 70 ° C. or lower, 9.84 parts of the compound obtained in (1) of Example 1 was gradually charged, and the reaction was carried out at 120 ° C. for 4 hours. Was. After cooling the reaction solution to 80 ° C., 9.52 parts of thionyl chloride was gradually added dropwise, and the reaction was carried out at the same temperature for 2 hours. The obtained reaction solution was poured into 200 parts of ice water to decompose the remaining chlorosulfonic acid and thionyl chloride. After the sulfurous acid in the liquid was eliminated with a hydrogen peroxide solution, the precipitated crystals were filtered and washed with 67 parts of ice water to obtain 35.0 parts of a wet cake.
(2) This was reacted with ammonia water in the same manner as in (3) of Example 1, and purified in the same manner to obtain 10.4 parts of a dried product (colorant mixture). This dye mixture has a β-substituted substance of 75% or more, a λmax in water of 603.0 nm, and is considered to have a sulfamoylation rate equivalent to that of the dye mixture obtained in Example 1 in consideration of other analysis results. Can be
This dye mixture had Cl ⁻ : 0.1% or less, SO ₄ ²⁻ : 0.1% or less, Fe: 100 ppm or less, Zn: 100 ppm or less, and Ca: 200 ppm or less.

Example 5 (evaluation of ink)
(A) Preparation of Ink The components shown in Table 1 below were mixed and dissolved, and filtered through a 0.45 μm membrane filter (manufactured by Advantech) to obtain an ink of the present invention. The water used was ion-exchanged water. Water and caustic soda (pH adjuster) were added so that the pH of the ink was pH = 8 to 10 and the total amount was 100 parts. The ink using the dye mixture of Example 1 was designated as C-1, and Examples 2 to 4 were also designated as C-2 to C-4 corresponding to the respective numbers.

Table 1
0.9 parts of each dye mixture obtained in Examples 1 to 4 0.9% water + caustic soda 80.0 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts IPA 3.0 parts Butyl carbitol 2.0 parts Surfynol 104 PG50 (surfactant) (manufactured by Nissin Chemical Co.) 0.1 part Total 100.0 parts

As comparative examples, dyes for inkjet recording used as Direct Blue 199, product name: Projet Cyan 1 (manufactured by Avesia: Comparative Example 1), and synthesis and purification by the method described in Example 1 of Patent Document 8 The resulting dye mixture (Comparative Example 2) was prepared by the same method so as to have the same print density as the C-1 to -4 inks during printing. The ink using the product of Comparative Example 1 was CA, and the ink using the dye mixture of Comparative Example 2 was CB.

(B) Ink-jet printing Using an ink-jet printer (trade name: BJ-S630, manufactured by Canon Inc.), a special paper (HR-101, a high-grade exclusive paper manufactured by Canon Inc.) and glossy paper (Professional Photo Paper PR-101, manufactured by Canon Inc.) are used. Two types were subjected to ink jet recording.

(C) Evaluation of recorded image Hue evaluation The hue of a recorded image is determined by measuring the color of a recording paper using a colorimetric system (GRETAG SPM50: manufactured by GRETAG), and determining the a ^* and b ^* values when L ^{* of} the printed matter is in the range of 50 to 90. The color was measured. The evaluation was performed in three steps, with the preferred a ^* value defined as -50 to -10 and the b ^* value defined as -50 to -10.
：: Both a ^* and b ^* values are present in a preferable region. Δ: Only one of a ^* and b ^* values is present in a preferable region. ×: Both a ^* and b ^* values are present outside a preferable region.

2. The test piece of the image recorded in the light fastness test was irradiated with a xenon weather meter (Model: CI4000, manufactured by ATLAS) at an illuminance of 0.36 W / m 2 for 50 hours under the conditions of a tank temperature of 24 ° C. and a humidity of 60% RH. After the test, with the reflection density (D value) in the range of 0.70 to 0.85, the reflection density before and after the test was measured using a colorimetric system. After the measurement, the dye residual ratio was calculated by (reflection density after test / reflection density before test) × 100 (%), and evaluated in three steps.
：: Residual rate 70% or more △: Residual rate 50 to 70%
×: Residual rate less than 50%

3. The test piece of the image recorded in the ozone resistance test was left for 3 hours at an ozone concentration of 12 ppm, a temperature in the tank of 24 ° C., and a humidity of 60% RH using an ozone weather meter (model OMS-H manufactured by Suga Test Instruments Co., Ltd.). After the test, with the reflection density (D value) in the range of 0.70 to 0.85, the reflection density before and after the test was measured using a colorimetric system. After the measurement, the dye residual ratio was calculated by (reflection density after test / reflection density before test) × 100 (%), and evaluated in three steps.
：: Residual rate 70% or more △: Residual rate 40 to 70%
×: Residual rate less than 40%

4. The test piece of the image recorded in the humidity resistance test was left at room temperature of 50 ° C. and humidity of 90% RH for 3 days using a thermo-hygrostat (Applied Giken Sangyo Co., Ltd.). After the test, the bleeding of the test piece was visually evaluated in three stages.
：: No bleeding observed Δ: Slight bleeding observed ×: Large bleeding observed

Table 2 shows the hue evaluation, the light resistance test result, the ozone resistance test result, and the moisture resistance test result of the recorded images of the inks (C-1 to C-4) using the dye mixtures obtained in Examples 1 to 4, respectively. (Special paper) and Table 3 (glossy paper).

Table 2
Ink evaluation result: Special paper ink number Hue Light resistance Ozone resistance Moisture resistance C-1 ○ ○ ○ ○
C-2 ○ ○ ○ ○
C-3 ○ ○ ○ ○
C-4 ○ ○ ○ ○
CA ○ ○ × ○
CB ○ ○ × ○

Table 3
Ink evaluation result: Glossy paper ink number Hue Light resistance Ozone resistance Moisture resistance C-1 ○ ○ ○ ○
C-2 ○ ○ ○ ○
C-3 ○ ○ ○ ○
C-4 ○ ○ ○ ○
CA ○ ○ × ○
CB ○ ○ × ○

As is clear from Tables 2 and 3, the cyan ink using the dye mixture of the present invention is excellent in hue, light resistance, ozone resistance and moisture resistance. In particular, it is clear that the ozone resistance is excellent.

Example 2 (ink set)
An ink-jet printer (BJ-F850 manufactured by Canon Inc.) having a cyan ink set in which two kinds of densities of light cyan and dark cyan are set is used. C-1 is used as the light cyan ink and Canon is used as the dark cyan ink. Inkjet recording was performed on two types of paper, genuine cyan ink, and special paper (HR-101, a high-grade paper manufactured by Canon Inc.) and glossy paper (PR-101, a professional photo paper manufactured by Canon Inc.). As for the printing result, a clear printed matter was obtained in which no missing dots or the like were generated and satisfactory for full-color image printing. As a result, it was confirmed that the ink of the present invention can be used for an inkjet printer having a cyan ink set in which two types of densities of light cyan and dark cyan are set.

The ink using the dye mixture of the present invention has an excellent hue as a cyan ink and is excellent in light fastness, ozone fastness and moisture fastness. In addition, storage stability is good without crystal precipitation, physical property change, color change, etc. after storage for a long time. Further, when used together with other magenta ink and yellow ink, it is possible to color tone in a wide visible region. The dye mixture of the present invention can be produced at low cost without using a particularly difficult method. Therefore, the cyan ink using the dye mixture of the present invention is extremely useful as an ink for inkjet recording.

Claims (16)

A mixture of dyes represented by the following formula (1)

[Wherein, R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ , and R ₁₅ each independently represent an unsubstituted sulfamoyl group (—SO ₂ NH ₂ ), a sulfone group (—SO ₃ M) or a hydrogen atom. However, at least one of R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ is an unsubstituted sulfamoyl group. R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ , and R ₁₆ represent a hydrogen atom, M represents a proton, an alkali metal ion, an alkaline earth metal ion, an onium ion of an organic amine or Ammonium ions are shown respectively. ] In each combination of R ₂ and R ₃ , R ₆ and R ₇ , R ₁₀ and R ₁₁ , and R ₁₄ and R ₁₅ , one is a hydrogen atom and the other is an unsubstituted sulfamoyl group (—SO ₂ NH ₂ ) or a sulfone group (-SO ₃ M), and _{R 2, R 3, R 6} , R 7, R 10, R 11, among of R _14, R _15, at least one is a non-substituted sulfamoyl group A mixture of the dyes according to claim 1. A compound represented by the following formula (2) or a salt thereof is reacted with a chlorinating agent, the sulfone group is replaced with a chlorosulfone group, and the compound is represented by the formula (1) obtained by reacting with an amidating agent. 3. A mixture of dyes according to claim 1 or claim 2

[In the formula, M represents a proton, an alkali metal ion, an alkaline earth metal ion, an onium ion or an ammonium ion of an organic amine. a, b, c, and d are 0 or 1, and the sum thereof is an integer of 1 to 4. ] A chlorinating agent is allowed to react with a compound obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a copper compound, and a chlorinating agent is reacted with the chlorosulfonic acid to form A mixture of dyes obtained by reacting an amidating agent after An ink comprising the dye mixture according to any one of claims 1 to 4 as a dye component. The ink according to claim 5, comprising a water-soluble organic solvent. The ink according to claim 5, which is for inkjet recording. 8. An ink set comprising: an ink jet printer using two or more kinds of cyan inks having different dye concentrations, wherein at least one kind uses the ink according to any one of claims 5 to 7. An ink set using an ink according to any one of claims 5 to 7 as an ink having the lowest dye concentration in an ink jet printer using two or more types of cyan inks having different dye concentrations. An ink jet recording method for ejecting ink droplets in accordance with a recording signal to record on a recording material, wherein the ink or the ink set according to any one of claims 5 to 9 is used. Recording method The inkjet recording method according to claim 10, wherein the recording material is an information transmission sheet. The ink jet recording method according to claim 11, wherein the information transmission sheet is a surface-treated sheet, and has an ink image receiving layer containing white inorganic pigment particles on a support. A container containing the ink or the ink set according to any one of claims 5 to 9. An inkjet printer having the container according to claim 13. A colored body colored using the ink or the ink set according to any one of claims 5 to 9. A chlorinating agent is reacted with a compound obtained by reacting a 4-sulfophthalic acid derivative or a 4-sulfophthalic acid derivative with a (phthalic anhydride) phthalic acid derivative in the presence of a copper compound to react a chlorinating agent with For producing a mixture of dyes obtained by reacting an amidating agent after