TW201237111A

TW201237111A - Ink composition, inkjet recording method and colored body

Info

Publication number: TW201237111A
Application number: TW100146292A
Authority: TW
Inventors: Akira Kawaguchi; Takashi Yoshimoto; Kenji Ooshima; Hirokazu Kitayama
Original assignee: Nippon Kayaku Kk
Priority date: 2010-12-17
Filing date: 2011-12-14
Publication date: 2012-09-16
Also published as: JP5814260B2; JPWO2012081637A1; TWI477562B; WO2012081637A1

Abstract

This ink composition contains a pigment (I), which is at least one type of pigment represented by formula (1), a tautomer thereof, or a salt of the pigment or tautomer, and a pigment (II), which is at least one type of pigment represented by formula (2) or a salt thereof. In formula (1), R1 represents a C1-C4 alkyl group or the like; R2 represents a cyano group or the like; R3 and R4 independently represent a hydrogen atom, a sulfo group, or a C1-C4 alkoxy group or the like; R5 and R7 independently represent a C1-C4 alkylthio group or the like; R6 and R8 independently represent a C1-C4 alkyl carbonyl amino group; R9 and R10 independently represent a C1-C4 alkoxy group or the like; and R11 to R13 independently represent a hydrogen atom, a sulfo group or the like. In formula (2), A and B independently represent a phenyl group or the like, which may have a substituent.

Description

201237111 六、發明說明：【發明所屬之技術領域】本發明係有關—種墨水組成物、喷墨記錄方法及著色體，該墨水組成物係包含至少特定兩種色素亦即色素（I)、 (II) ’該喷墨S己錄；法係使用該墨水組成物，該I色體係藉由該墨水組成物所著色。【先前技術】在各種彩色記錄方法中，作為具有代表性的方法之一之藉由喷墨印表機來進行之記錄方法，為使墨水之液滴產 f ’並使該液滴附著在各種被記錄材料(紙、薄膜、布匹 ')進行。己錄。此方法係由於記錄頭與被記錄材料不會直接接觸，故較少路φ殼^ i 發出聲日而較安靜。此外，該方法係由於/、有谷易進行，丨、刑/μ . .n ^'化、尚速化之特徵，故近年來正迅速，曰及，亦期待今後有大幅增長。墨水以Π鋼筆或簽字筆用等之墨水、以及喷墨記錄用之色辛溶二：：用"'種水性墨水，該水性墨水係使水溶性 ”而成。在此等水性墨水中，-般添加性有機溶劑，以防止墨窠。而S $ &任聿尖或墨水噴出喷嘴堵塞而且，對於此等墨水要炎.&执從德 τ a 要求.能夠獲得濃度充分的記錄圖像、不會發生筆尖或喷刀的。己錄良好、參暈較少、計—土被記錄材料上乾燥性之水溶性色素特別要求：dr此外’對於所使用〃對水之溶解度高、對墨水中所 201237111 添加之水溶性有機溶劑之溶解度之圖像要求：耐水性、，纟’對於所形成牢固性。、耐氣體性、耐濕性等圖像 v 此等令，所謂耐氣體性在於空氣中之具有氧化作用之= 曰對I述現象之耐性：存色素產生作用，而使所、^專在被記錄材料中對邱之圖像變/褪色。除了彝惫备，、，外，具有此種作用之氧化性0 * 于了昊氧就Μ 但此等氧化性氣體中:’皇、可列舉N〇X、S〇X等’ ==色現象…物質。，有耐氣二 =:Γ氧氣性之傾向。於相片晝質之喷墨專用紙之 ==墨水接受層’大多使用多孔性白色無機物等材一，以加快墨水乾燥並減少高晝質下之渗晕。在這樣的記錄紙上，能夠顯著觀察到由臭氣氣所造成之變/提色。由於此由氧化性氣體所造成之變/趣色現象，對於嘴墨記錄圖像而§為特徵性的現象，故提高耐臭氧氣性，成為喷墨記錄方法中最重要的課題之一。為了今後擴大使用墨水之印刷方法之使用領域，對於進行喷墨記錄時所使用之墨水組成物、及藉由該墨水組成物所著色之著色體，強烈要求更加提高：耐光性、❹氧氣性、耐濕性、耐·水性。各種色相的墨水係由各種色素所調製，該等令，累色墨水為使用於單色圖像及全彩圖像兩者之重要墨水。然然已進行，該色素而’開發下述色素在技術性上困難點相當多，雖大量的研究開發，但具有充分性能之色素仍很少 201237111 係濃色域及淡色域為中 « . ,0 ^ , .β , 的色相，且列印濃度高，並且呈現色相的先源相關性較 % μ β ^ ^ 良好的黑色。因此，一般調配禝数禋多種色素來調製里 . …、色^水。然而，若混合複數種色 y 素來調製墨水，則相較、^單一色素來調製墨水時，更會有下述問碭：（1)色相會人媒；丨（被屺錄材料）而異、（2)會因色素受到光或臭氧氣m八、軋氣所分解而特別使變色情形變嚴重等。並且’在混合複數種色辛匕系术調製墨水時，為了混合多種色素，而發生下述問題· •…色色素在墨水中所佔之比例降低，而列印濃度降低。万面，右為了抑制列印濃度降低而增加墨水中之由各从“ '^ /u 甲之色素的總量，則會發生泛金光 (bronzmg)現象，而成為乍為黑色印刷物之品質降低之原因。因此，要求開路τ ;+. A * 開發下述色素：列印濃度高的色素、和耐泛金光性良好的色辛，伯曰& 巴京但目刚具有充分性能之色素仍很少。此處’所謂泛金光現象參 ^ 係知下述現象：因色素凝集和墨水吸收不良等眉因 A ” 寻席因色素在被記錄材料之表面上成為金屬片狀’而發生閃爍。若發生此現象，則在光澤性、列印品質、列印濃度所有的觀點上均不良。特料，在使用金屬駄菁系色素或多偶氮系色素作為色素進行列印分’常會顯現「泛紅現象」，使圖像整體之色平衡變得不均勻，而使圖像品質降低。此外，千术大夕使用光澤紙作為具有接近相片畫質的質感之被記錄材料，但若發生泛金光現象，則記錄物表面之光澤感會發生不均勻，而顯損害圖像的質感。從這樣的觀點來看，強烈期望—種色素者其係不會發生泛金光現象》 μ 201237111 印刷物之各種耐久性良可舉例如專利文獻1之墨水種墨水，其係更加改良耐臭好。然而，此等墨水為一種刷物之圖像牢固性大幅進行氧氣性進一步進行改善，而要求之製品。好的喷墨用黑色墨水組成物，。此外’專利文獻2係提案— 氧性’且作為黑色之色相亦良墨水組成物，其係亦經針對印改良’但正期望特別針對耐臭尚無法提供一種充分滿足市場 [先前技術文獻] (專利文獻）專利文獻1 ··國際公開第2007/077931號專利文獻2 :日本特開2〇〇9_185133號公報專利文獻3 :國際公開第2006/001274號專利文獻4 :國際公開第2008/〇53：776號專利文獻5 :日本專利第33 83 469號公報專利文獻6 :德國專利發明第2〇〇4488號說明書【發明内容】 [發明所欲解決之問題] , 本發明之目的在於提供一種水性黑色墨水組成物，其 v 係即使長時間保存仍安定，並且在進行濃色印刷及淡色印刷時之任一情形’均呈現彩度低且無色調之中性的黑〜灰所歹j p之圖像的遭度高，而能夠獲得一種黑色記錄圖像’戎黑色記錄圖像之記錄圖像的各種牢固性非常優 201237111 異，特別是耐臭氧氣性非常優異。 [解決問題之技術手段] . 本發明人等係為了解決如上所述之問題而反覆致力進 ▼ 行研究後，結果發現一種墨水組成物能夠解決上述問題，遂完成本發明，該墨水組成物係包含：至少一種的特定式 (1)所示之色素、其互變異構物、或該等之鹽（色素（1));至少一種的式（2)所示之色素或其鹽（色素（π))。換言之，本發明係有關下述。 1) 一種墨水組成物，其係包含：色素（1)、及色素（„)，該色素（I)為至少一種的下述式（1)所示之色素、其互變異構物、或該等之鹽，該色素（„)為至少一種的下述式（2)所示之色素或其鹽：201237111 VI. Description of the Invention: [Technical Field] The present invention relates to an ink composition, an inkjet recording method, and a coloring body, the ink composition comprising at least two specific pigments, namely, a pigment (I), II) 'The ink jet has been recorded; the method uses the ink composition, and the I color system is colored by the ink composition. [Prior Art] Among various color recording methods, a recording method by an ink jet printer as one of representative methods produces a droplet of ink and causes the droplet to adhere to various types. It is carried out by recording materials (paper, film, cloth '). Recorded. This method is because the recording head does not directly contact the material to be recorded, so that less roads φ shells emit sound and are quieter. In addition, this method is characterized by the fact that it has been carried out by /, and it has been characterized by 谷, 刑, / . . . 、、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The ink is ink such as a sputum pen or a signature pen, and the color of the ink for inkjet recording is two: using "'a kind of aqueous ink, the aqueous ink is made water-soluble. In these aqueous inks, - Adding organic solvents to prevent ink sputum. S $ & 聿 tip or ink ejector nozzle is clogged and it is inflammatory for these inks. &; 德德 τ a . . . . . . . . . . . . . . τ Like, there will be no pen tip or squeegee. The well-recorded, less faint, water-soluble pigments on the soil-recorded material are particularly required: dr in addition to the solubility of the hydrazine used in water, The image of the solubility of the water-soluble organic solvent added in 201237111: water resistance, 牢固' for the formation of firmness, gas resistance, moisture resistance, etc. v. The so-called gas resistance is Oxidation in the air = 耐 resistance to the phenomenon of I: the effect of the pigment, so that the image of the Qi in the recorded material is changed / faded. In addition to preparation,,,, Have such a role Oxidation 0 * In the case of oxygen, but in these oxidizing gases: 'Emperor, can be listed N〇X, S〇X, etc.' == color phenomenon... substance. The tendency is to use a porous white inorganic material such as the ink-receiving layer of the inkjet paper of the photo enamel to accelerate the drying of the ink and reduce the turbidity under high enamel. On such recording paper, it is remarkable. The change/coloring caused by the odor gas is observed. Due to the change/fun color phenomenon caused by the oxidizing gas, the image is recorded as a characteristic phenomenon for the ink of the mouth, so that the ozone gas resistance is improved. One of the most important issues in the inkjet recording method. In order to expand the field of use of the printing method using ink, the ink composition used for inkjet recording and the color body colored by the ink composition Strongly demanding more improvement: light resistance, oxygen resistance, moisture resistance, water resistance. Various color inks are prepared by various pigments. These colors are used for monochrome images and full color images. Like the important ink of both. However, the pigment has been developed, and the development of the following pigments is technically difficult. Although a large amount of research and development has been carried out, the pigments with sufficient properties are still very few 201237111. The color gamut and the light color gamut are in the middle « . , 0 The hue of ^ , .β , and the high print density, and the hue correlation of the hue is better than that of % μ β ^ ^. Therefore, the number of pigments is generally adjusted to modulate a variety of pigments. However, if a plurality of colors of y is mixed to modulate the ink, when the ink is prepared by a single coloring, the following questions are asked: (1) the hue will be human; the 丨 (the material being smeared) may vary. (2) The discoloration of the pigment may be severely caused by the decomposition of the pigment or the ozone gas, and the gas is decomposed. Further, in the case of mixing a plurality of kinds of chromophores, the following problems occur in order to mix a plurality of pigments. • The proportion of the coloring matter in the ink is lowered, and the printing density is lowered. In order to suppress the decrease in the printing density, the right bronzmg phenomenon occurs in the ink from the total amount of the pigment of '^^u, and the quality of the black printed matter is lowered. Therefore, it is required to open the circuit τ; +. A * Develop the following pigments: printing pigments with high concentration, and coloring with good bronzing resistance, Boss & Bajing, but the pigments with sufficient performance are still very Here, the term "the phenomenon of the bronzing phenomenon" is known as follows: the eyebrow cause A due to pigment aggregation and ink absorption is flickered due to the fact that the pigment becomes a metal sheet on the surface of the material to be recorded. If this happens, it is not good in terms of glossiness, print quality, and print density. In particular, when a metal phthalocyanine-based dye or a polyazo-based dye is used as a dye to perform a printing process, the "redness phenomenon" often occurs, and the color balance of the entire image becomes uneven, and the image quality is lowered. In addition, Glossy uses a glossy paper as a material to be recorded which has a texture close to the photographic quality. However, if a golden phenomenon occurs, the glossiness of the surface of the recorded object may be uneven, which may impair the texture of the image. From such a viewpoint, it is strongly desired that the pigmentation does not cause a bronzing phenomenon. μ 201237111 Various durability of the printed matter is good. For example, the ink of the ink of Patent Document 1 is more excellent in odor resistance. However, such inks are a product which is required to further improve the oxygenity of the image of the brush. Good inkjet with black ink composition, . In addition, 'patent document 2 proposes - oxygenity' and as a black hue ink composition, which is also improved for printing', but it is expected that it is not particularly suitable for the odor resistance, and it is not sufficient to satisfy the market [previous technical literature] [Patent Document 1] Patent Document 1: International Publication No. 2007/077931 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document No. 776: Japanese Patent No. 33 83 469, Patent Document 6: German Patent No. 2, 4,488, entitled [Problems to be Solved by the Invention], an object of the present invention is to provide an aqueous solution. The black ink composition, the v system is stable even after long-term storage, and in any case when performing rich color printing and light color printing, both of them have a low chroma and a colorless neutral black to gray. The image has a high degree of suffering, and it is possible to obtain a black recorded image. The recorded image of the black recorded image has excellent robustness to 201237111, especially ozone resistance. different. [Means for Solving the Problems] The present inventors have repeatedly made efforts to solve the above problems, and as a result, have found that an ink composition can solve the above problems, and the ink composition system is completed. And comprising: at least one pigment represented by the specific formula (1), a tautomer thereof, or a salt thereof (pigment (1)); at least one pigment represented by the formula (2) or a salt thereof (pigment ( π)). In other words, the invention relates to the following. 1) An ink composition comprising: a dye (1) and a pigment (I), wherein the dye (I) is at least one of a dye represented by the following formula (1), a tautomer thereof, or a salt or the like, wherein the pigment („) is at least one of the dyes represented by the following formula (2) or a salt thereof:

[式⑴中， R丨表不：（C1〜C4)烷基；經羧基所取代之（C1〜C4)烷基；笨基；經磺基所取代之苯基；或羧基， R2表示：氰基；胺甲醯基；或羧基， R3及R4分別獨立地表示：氫原子；（C1〜C4)烷基；鹵素原子；（C1〜C4)烷氧基；或磺基， R表不：（C1〜C4)烷硫基；或經從由羥基、磺基及羧基所構成之群組中選出之至少一種基所取代之（C1〜C4)烷 201237111 硫基’ r6表示（Cl〜C4)烷基羰基胺基， R7表示：（C1〜C4)烷硫基；或經從由羥基、磺基及羧基所構成之群組中選出之至少一種基所取代之（C 1〜C4)烷硫基， R8表示（C1〜C4)烷基羰基胺基， R9及R1G分別獨立地表示：氫原子；羧基；磺基；乙醯基胺基；氯原子；（C1〜C4)烷基；（C1〜C4)烷氧基；或經從由經基、（C1〜C4)烷氧基、磺基及羧基所構成之群組中選出之至少一種基所取代之（C]〜C4)烷氧基， R11〜R13分別獨立地表示：氫原子；羧基；磺基；羥基；乙醯基胺基；氯原子；氰基；硝基；胺磺醯基；（C1 〜C4)烷基；（Cl〜C4)烷氧基；經從由羥基、（ci〜C4)烷氧基、磺基及羧基所構成之群組中選出之至少一種基所取代之（C1〜C4)烷氧基；（C1〜C4)烷磺醯基；或經從由羥基、磺基及羧基所構成之群組中選出之至少一種基所取代之 (C1〜C4)烷磺醯基][In the formula (1), R 丨 represents: (C1 to C4) alkyl; (C1 to C4) alkyl substituted by a carboxyl group; stupid; phenyl substituted by a sulfo group; or a carboxyl group; R2 represents: cyanide Or an indenyl group; or a carboxyl group, R3 and R4 each independently represent: a hydrogen atom; (C1 to C4) alkyl; a halogen atom; (C1 to C4) alkoxy; or a sulfo group, R represents: a C1-C4 alkylthio group; or a (C1~C4) alkane substituted with at least one group selected from the group consisting of a hydroxyl group, a sulfo group and a carboxyl group; 20123711, a sulfur group 'r6' represents a (Cl~C4) alkane a carbonylamino group, R7 represents: a (C1 to C4) alkylthio group; or a (C 1 - C4) alkylthio group substituted with at least one selected from the group consisting of a hydroxyl group, a sulfo group and a carboxyl group; R8 represents a (C1 to C4) alkylcarbonylamino group, and R9 and R1G each independently represent a hydrogen atom; a carboxyl group; a sulfo group; an ethyl hydrazino group; a chlorine atom; (C1 to C4) alkyl group; a C4) alkoxy group; or a (C)-C4) alkoxy group substituted with at least one group selected from the group consisting of a group consisting of a (C1 to C4) alkoxy group, a sulfo group and a carboxyl group; R11~R13 are independent Ground: hydrogen atom; carboxyl group; sulfo group; hydroxyl group; ethyl hydrazino group; chlorine atom; cyano group; nitro group; amine sulfonyl group; (C1 to C4) alkyl group; (Cl~C4) alkoxy group; (C1~C4) alkoxy group substituted by at least one group selected from the group consisting of a hydroxyl group, a (ci~C4) alkoxy group, a sulfo group and a carboxyl group; (C1 to C4) alkanesulfonyl group Or (C1 to C4) alkanesulfonyl group substituted with at least one selected from the group consisting of a hydroxyl group, a sulfo group and a carboxyl group;

[式（2)中， A及B分別獨立地表示：苯基；萘基；或具有1個偶氮鍵之基，該等基可經從由羥基、磺基、羧基、及（C1~C4) 烷基羰基胺基所構成之群組中選出之至少一種基所取代]。 201237111 2) 如上述1)所述之墨水組_成物，其中，在前述式（1)中， R為曱基或笨基， R2為氰基或胺曱醯基， R3為氫原子；曱基；或曱氧基， R4為磺基， R5為經磺基或羧基所取代之（C1〜C4)烷硫基， R6為（C1〜C4)烷基羰基胺基， R7為經磺基或羧基所取代之（c i〜C4)烷硫基， R8為（C1〜C4)烷基羰基胺基， R9為磺基（C1〜C4)烷氧基， R1G為（C1〜C4)烷基或乙醯基胺基， R11〜R13分別獨立地為：氫原子；羧基；磺基；氯原子；硝基；曱基；曱氧基；胺磺醯基；或是經磺基或羧基所取代之（C1〜C4)烷磺醯基。 3) 如上述1)所述之墨水組成物，其中，在前述式（2)中， A及B分別獨立地為：具有從由磺基及羧基所構成之群組中選出之至少一種取代基且具有“固偶氮鍵之基。 4) 如上述1)所述之墨水組成物，其中，復包含：色素（iii) 及色素(no之至少一者’該色素⑽為下述式⑴所示之色素或其鹽’該色素（IV)為水溶性黃色染料，該水溶性黃色染料係不包含在上述式⑴〜(1„)中且i分子中具有卜偶氮基： 9 201237111 so3h so3h ^^^_Ν=Ν_<ζ^-Ν=Ν-〇-ΝγΝγΝ-^Λ-Ν=Ν-^Ι^-Ν=Ν-^^[In the formula (2), A and B are each independently represented by a phenyl group; a naphthyl group; or a group having one azo bond, which may be derived from a hydroxyl group, a sulfo group, a carboxyl group, and (C1 to C4). Substituting at least one selected from the group consisting of alkylcarbonylamino groups]. 201237111 2) The ink set according to the above 1), wherein, in the above formula (1), R is a fluorenyl group or a stupid group, R 2 is a cyano group or an amine fluorenyl group, and R 3 is a hydrogen atom; Or a decyloxy group, R4 is a sulfo group, R5 is a (C1~C4)alkylthio group substituted by a sulfo group or a carboxyl group, R6 is a (C1~C4)alkylcarbonylamino group, and R7 is a sulfo group or a (ci~C4)alkylthio group substituted by a carboxyl group, R8 is a (C1~C4)alkylcarbonylamino group, R9 is a sulfo(C1~C4)alkoxy group, R1G is a (C1~C4)alkyl group or a a mercaptoamine group, R11 to R13 are each independently: a hydrogen atom; a carboxyl group; a sulfo group; a chlorine atom; a nitro group; an anthracenyl group; an anthraceneoxy group; an aminesulfonyl group; or a sulfo group or a carboxyl group; C1 to C4) alkanesulfonyl. 3) The ink composition according to the above 1), wherein, in the above formula (2), A and B are each independently at least one substituent selected from the group consisting of a sulfo group and a carboxyl group. The ink composition according to the above-mentioned 1), which further comprises: a dye (iii) and a pigment (at least one of the 'n' of the dye (10) is represented by the following formula (1) The pigment (IV) is a water-soluble yellow dye which is not contained in the above formulas (1) to (1) and has a azo group in the i molecule: 9 201237111 so3h so3h ^^^_Ν=Ν_<ζ^-Ν=Ν-〇-ΝγΝγΝ-^Λ-Ν=Ν-^Ι^-Ν=Ν-^^

J 丫 VJ 丫 V

X (3) [式（3)中，X (3) [in equation (3),

Ra表示：氫原子；羥基；羧基；無取代（Cl〜C4)烷基；經羥基或（C1〜C4)烷氧基所取代之（C1〜C4)烷基；無取代 (C1〜C4)烷氧基；經羥基或（C1〜C4)烷氧基所取代之（C1 〜C4)烷氧基；無取代（ci〜C4)烷基胺基；經羥基或（C1〜 C4)烷氧基所取代之（C1〜C4)烷基胺基；羧基（C1〜C5)烷基胺基；雙（羧基（C1〜C5)烷基）胺基；無取代（C1〜C4)烷醯基胺基；經羥基或（C1〜C4)烷氧基所取代之（C1〜C4)烷醯基胺基；無取代苯基胺基；苯環經從由羧基、磺基及胺基所構成之群組中選出之至少一種基所取代之苯基胺基；磺基，鹵素原子；或腺基， X表示經羧基或磺基所取代之脂肪族胺基]。 5) 如上述4)所述之墨水組成物，其中，前述式（3)所示之色素係如下述式（4)所示： so3h H03S-^~~N=N—N=N h3cRa represents: a hydrogen atom; a hydroxyl group; a carboxyl group; an unsubstituted (Cl-C4) alkyl group; a (C1 to C4) alkyl group substituted by a hydroxyl group or a (C1 to C4) alkoxy group; an unsubstituted (C1 to C4) alkane (C1 ～C4) alkoxy group substituted by hydroxy or (C1~C4) alkoxy group; unsubstituted (ci~C4)alkylamino group; via hydroxyl group or (C1~C4) alkoxy group Substituted (C1~C4)alkylamino group; carboxy(C1~C5)alkylamino group; bis(carboxy(C1~C5)alkyl)amino group; unsubstituted (C1-C4) alkanoylamino group; a (C1~C4) alkanoylamino group substituted by a hydroxy group or a (C1-C4) alkoxy group; an unsubstituted phenylamino group; the benzene ring is from a group consisting of a carboxyl group, a sulfo group and an amine group a phenylamine group substituted with at least one selected group; a sulfo group, a halogen atom; or a gland group, X represents an aliphatic amine group substituted with a carboxyl group or a sulfo group]. (5) The ink composition according to the above (4), wherein the dye represented by the above formula (3) is represented by the following formula (4): so3h H03S-^~~N=N-N=N h3c

%NY^'O-N=N"O~N=N-(^'S03H ch3%NY^'O-N=N"O~N=N-(^'S03H ch3

X ⑷ [式（4)中， X表示：具有羧基或磺基之單（C1〜C5)烷基胺基、或是具有羧基或磺基之二（C1〜C5)烷基胺基]。 6) 如上述4)所述之墨水組成物，其中，包含前述色素（ΠΙ) 201237111 及前述色素（ιν)兩者。 7) 如上述D所述之墨水組成物，其中，在墨水組成物中所含之色素的總質量中，前述色素（I)之比例為5〇〜9〇質量 % ’前述色素（II)之比例為1〜10質量％。 8) 如上述D所述之墨水組成物，其中，相對於墨水組成物的總質量，前述色素⑴及前述色素（11)的總含量為〇1〜 20質量％。 9) 如上述6)所述之墨水組成物，其中，墨水組成物中所含之色素的總質量中，前述色素⑴之比例為5〇〜9〇質量 %，前述色素（II)之比例為}〜！0質量％，前述色素（ΙΠ)之比例為5〜20質量％，前述色素（IV)之比例為4〜2〇質量 % » 、里 Μ)如上述6)所述之墨水組成物，其中，相對於墨水組成物的總質量，前述色素⑴、前述色素（11)、前述色素（πι) 及前述色素（IV)的總含量為01〜20質量％。 1 υ如上述1)所述之墨水組成物，其係用於進行噴墨記錄。 12) 一種喷墨記錄方法，其係使用上述1}至η)中任一項所述之墨水組成物作為墨水，使該墨水之墨水滴因應記錄訊號來噴出，而在被記錄材料進行記錄。 )如上述12)所述之喷墨記錄方法，其中，前述被記錄材料為資訊傳遞用片材。 )如上述13)所述之喷墨記錄方法，其中，前述資訊傳遞用片材為具有墨水接受層之片材，該墨水接受層係包含多孔性白色無機物。 201237111 1 5) 一種著色體’其係藉由上述1)至11)中任一項所述之墨水組成物所著色。 • 1 6. 一種喷墨印表機’其係裝填有容器，該容器係包含上 f 述丨）至11)中任一項所述之墨水組成物。 [功效] 本發明之墨水組成物，係長時間保存後不會發生結晶析出、物性變化、色變化等，而儲存安定性良好。此外，當使用本發明之墨水組成物作為墨水，在喷墨專用紙進行記錄時，列印濃度亦高，各種牢固性優異，特別是耐臭氧氣性優異。如上所述，本發明之昼水組成物，係極有用於作為喷墨記錄用黑色墨水。【實施方式】 [實施發明的較佳形態] 以下，詳細說明本發明。再在本說明書中，只要未特別說明，確基、缓基等酸性官能基即是以游離酸之形態來表示。此外，為了避免記載過於繁雜 n 1豕巴常、其互轡1 冓物、或該等之鹽」般的記、載為「务夺/ 虿時為了方便而僅簡略記施 Λ j &素其互變異構物、該蓉夕鹽、該等之混合物之任一者。 ·"等之同樣地’為了避免記載過於繁雜，像般的記截，右&京'或其鹽」時為了方便而簡略記載戰為色素」，但此時亦 12X (4) [In the formula (4), X represents a mono(C1-C5)alkylamino group having a carboxyl group or a sulfo group, or a di(C1-C5)alkylamino group having a carboxyl group or a sulfo group]. 6) The ink composition according to the above 4), which comprises both the coloring matter (ΠΙ) 201237111 and the coloring matter (ιν). (7) The ink composition according to the above-mentioned D, wherein the ratio of the dye (I) is 5 〇 to 9 〇 mass% of the total mass of the dye contained in the ink composition. The ratio is 1 to 10% by mass. 8) The ink composition according to the above D, wherein the total content of the dye (1) and the dye (11) is 〇1 to 20% by mass based on the total mass of the ink composition. (9) The ink composition according to the above (6), wherein the ratio of the dye (1) is 5 〇 to 9 〇 mass%, and the ratio of the dye (II) is the total mass of the dye contained in the ink composition. }~! 0% by mass, the ratio of the coloring matter (ΙΠ) is 5 to 20% by mass, and the ratio of the coloring matter (IV) is 4 to 2% by mass. The ink composition according to the above 6), wherein The total content of the dye (1), the dye (11), the dye (πι), and the dye (IV) is from 01 to 20% by mass based on the total mass of the ink composition. An ink composition as described in the above 1), which is used for inkjet recording. 12) An ink jet recording method using the ink composition according to any one of the above 1} to η) as an ink, and ejecting ink droplets of the ink according to a recording signal to perform recording on a material to be recorded. The ink jet recording method according to the above 12, wherein the recording material is a sheet for information transmission. The ink jet recording method according to the above 13), wherein the information transfer sheet is a sheet having an ink receiving layer containing a porous white inorganic material. 201237111 1 5) A coloring body' which is colored by the ink composition according to any one of the above 1) to 11). 1. An ink jet printer that is loaded with a container, the container comprising the ink composition of any one of the above-mentioned items. [Efficacy] The ink composition of the present invention does not cause crystal precipitation, physical property change, color change, etc. after long-term storage, and has good storage stability. Further, when the ink composition of the present invention is used as an ink, when printing on an ink jet paper, the printing density is also high, and various kinds of fastness are excellent, and in particular, ozone resistance is excellent. As described above, the hydrophobic composition of the present invention is extremely useful as a black ink for inkjet recording. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. Further, in the present specification, an acidic functional group such as a confirming group or a slow-base group is represented by a form of a free acid unless otherwise specified. In addition, in order to avoid the description that the description is too complicated, the ones are the same as the ones, or the salt is the same as the ones, and the words are only for the sake of convenience. Any of the tautomers, the sulphate salts, and the like. · "etc. The same 'in order to avoid the description is too complicated, like the interception, right & Jing' or its salt" For the sake of convenience, simply describe the war as a pigment, but at this time also 12

V 201237111 意指色素、其鹽、該等之混合物之任一者。本發明之墨水組成物為一種水性之黑色墨水組成物，其特徵在於包含：至少一種的上述式（1)所示之色素（1)、至少一種的上述式（2)所示之色素（11)。此外，如後所述，經由復包含色素（III)及/或色素（IV)，即能夠使本發明之功效更属著。換5之，旎夠貫現一種墨水組成物，其係儲存安疋性、列印濃度、各種牢固性極優異。並且，為了調製中 I·生且冋。0質的黑色之目的，本發明之墨水組成物可復包含色素⑴、色素（II)、色素（III)及色素（IV)以外之色素。然而，一般情形中，本發明之墨水組成物，係即使不包含色素色素W、色素⑽及色切V)以外之色素，仍㈣獲得本發明之功效。本發明之墨水組成物所含之色素（1)，為一種以上的上 :式⑴所示之色素。換言之’色素⑴可為上述式⑴所示之 :色：，但從製造容易度、便宜等觀點來看，通常宜為 …該混合色素係由上述式⑴所示之的數種所構成，大虼而A ,, 购虱化口物佳，以2广 …1〜8種為佳，以1〜7種較〜6種更佳。再者，即使為這樣的混會對由本發明所得之功效造成任何妨礙。素’亦不上述式（1)所示之偶氮化合物係具有互變異構物，係险并構物。此互、除了上述式⑴所示之化合物下述式（5)、（^)笪, A r 亦可能為 (6)等。此等化合物亦包含在本勹式（5)及（6)申，R〗^ 月之内。再者， R〜R】3係具有與上述式( 石同的意義。之R〜R】3相 13 v 201237111V 201237111 means any of a pigment, a salt thereof, or a mixture thereof. The ink composition of the present invention is an aqueous black ink composition comprising at least one of the dye (1) represented by the above formula (1) and at least one of the dyes represented by the above formula (2) (11). ). Further, as will be described later, the effect of the present invention can be made more important by the complex inclusion of the dye (III) and/or the pigment (IV). In the case of 5, an ink composition is obtained, which is excellent in storage stability, printing density, and various firmness. Also, in order to modulate the I. For the purpose of zero-quality black, the ink composition of the present invention may further contain a pigment other than the pigment (1), the pigment (II), the pigment (III), and the pigment (IV). However, in general, the ink composition of the present invention obtains the effects of the present invention even if it does not contain a pigment other than the pigment dye W, the pigment (10), and the color cut V). The pigment (1) contained in the ink composition of the present invention is one or more of the above-mentioned dyes represented by the formula (1). In other words, the coloring matter (1) may be a color: as shown in the above formula (1), but it is generally preferable that the mixed coloring matter is composed of several types represented by the above formula (1) from the viewpoints of easiness of production, inexpensiveness, and the like.虼 A A , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Moreover, even such a mixture causes any hindrance to the effects obtained by the present invention. The azo compound represented by the above formula (1) also has a tautomer and is a structure. In addition to the compound represented by the above formula (1), the following formula (5), (^) 笪, A r may also be (6) or the like. These compounds are also included in the formula (5) and (6), R 〖 ^ month. Further, R to R] 3 has the same meaning as the above formula (the same meaning as the stone. R to R) 3 phase 13 v 201237111

上述式（1)中，R1中，（Cl〜C4)烷基可舉例如：直鏈或支鏈之無取代（C1〜C4)烷基，以直鏈為佳。具體例可舉例甲基乙基、正丙基、正丁基等直鏈（C1〜C4)烷基；異丙基、異了基、二級丁基、三級丁基等支鍵⑼〜以)烧基等。較佳具體例可舉例如：甲基、正丙基，以甲基特佳。 R中，經羧基所取代之（C1〜C4)烷基可舉例如：在上述無取代（CM〜C4)烧基之任—碳原子上取代錢基者。缓基的取代位置係無特別限制，較佳是取代在院基之末端，缓基之取代數為1或2個，以I個為佳。具體例可舉例如. 缓基甲基、2·絲乙基等。較佳具體例可舉例如㈣甲基。 R中，經續基所取代之苯基可舉例如：取代有h 個磺基之苯基’以〗或2個為佳，磺基的取代位置別限制：具體例可舉例如：3_續基苯基、4•樹基、二一續基笨基、3,5-二错基續基苯基。 ” HU佳具㈣可舉例如4· (C1 較佳的R1可舉例〜C4)烷基、苯基、如.（C〗〜C4)燒基、經羧基所取代經嗜基所取代之苯基。之 201237111 以（Cl〜C4)烧基、苯基、經續基所取代之苯基較佳。以（C1〜C4)烷基、笨基更佳。以（C1〜C4)烷基特佳，其中，以甲基最佳。上述式⑴中，R2表示n胺甲醯基；缝基。盆中，以氰基、胺甲酿基為佳，以氛基較佳。 ” 上述式（1)中’ R3及R4中，（C1〜C4)院基可舉例如：包含為佳者等在内’均與上述R1中之（C1〜C4)院基相同者。 R3及R4中’ i素原子可舉例如：氣原子、氣原子、漠原子、碘原子，以氣原子為佳。及R中’（C1〜C4)烧氧基可舉例如：直鏈或支鍵之無取代（C1〜(：4)烧氧基，以直鏈為佳。具體例可舉例如：甲氧基 '乙氧基、正丙氧基、正丁氧基等直鍵（ci〜C4)院氧基；異丙氧基、異丁氧基、二級丁氧基、三級丁氧基等支鍵（=1〜(：4)貌氧基p此等中，以甲氧基特佳。 R及R分別獨立地以氫原子、（C1〜C4)烷基、（C1〜 C4)烷氧基、或磺基為佳。以任一者為氫原子、另-者為續基之組合為佳。 R3及R4的取代位置係無特別限制，任一者為氮原子、另-者為料時，科基較佳是取代在：構成苯㈣唾并吼錢（benzimidazc)lQpyHd_)環之不鄰接任—氮原子之側的2個碳原子之任一者。從谷易口成及便且之觀點來看，本發明之上述式⑴所示之化合物可以下述形式使用：包含…及r4的取代位置 15 201237111In the above formula (1), in the case of R1, the (Cl~C4) alkyl group may, for example, be a linear or branched unsubstituted (C1-C4) alkyl group, preferably a straight chain. Specific examples thereof include a linear (C1-C4) alkyl group such as methylethyl, n-propyl or n-butyl; a branch (9) of isopropyl, iso-, di-butyl or tert-butyl; ) Burning base, etc. Preferable specific examples include methyl or n-propyl groups, and methyl groups are particularly preferred. In R, the (C1 to C4) alkyl group substituted by a carboxyl group may, for example, be a substituent substituted on the carbon atom of the above-mentioned unsubstituted (CM~C4) alkyl group. The substitution position of the buffer group is not particularly limited, and it is preferably substituted at the end of the hospital base, and the number of substitutions of the buffer group is 1 or 2, preferably 1 or more. Specific examples thereof include a thiomethyl group, a 2, a silk ethyl group and the like. A preferred embodiment is, for example, a (tetra)methyl group. In R, the phenyl group substituted by the repeating group may, for example, be a phenyl group substituted with h sulfo groups or two, and the substitution position of the sulfo group is not limited: specific examples include, for example, 3_ continued A phenyl group, a 4 phenyl group, a hexyl group, a 3,5-di-yl phenyl group. "Hujiajia (4)", for example, 4 (C1 preferably R1 can be exemplified to C4) alkyl, phenyl, such as (C) ~ C4), substituted by a carboxyl group substituted by a phenyl group 201237111 The phenyl group substituted with a (Cl~C4) alkyl group, a phenyl group and a contiguous group is preferred. The (C1~C4) alkyl group is more preferred, and the (C1~C4) alkyl group is particularly preferred. Among them, in the above formula (1), R2 represents an n-aminomethyl group; a slit group. In the pot, a cyano group or an amine group is preferred, and an atmosphere group is preferred. In the case of 'R3 and R4, the (C1 to C4) yards are the same as those of the above-mentioned R1 (C1 to C4). Examples of the "i" atom in R3 and R4 include a gas atom, a gas atom, a desert atom, and an iodine atom, and a gas atom is preferred. And the '(C1 to C4) alkoxy group in R may, for example, be a straight chain or a bondless unsubstituted (C1 to (:4) alkoxy group, preferably a straight chain. Specific examples include a methoxy group; 'Ethyloxy, n-propoxy, n-butoxy and other direct bonds (ci~C4) alkoxy; isopropoxy, isobutoxy, secondary butoxy, tertiary butoxy, etc. (=1~(:4)morphous oxyp. Among these, methoxy is particularly preferred. R and R each independently represent a hydrogen atom, a (C1 to C4) alkyl group, or a (C1 to C4) alkoxy group. Or a sulfo group is preferred. It is preferred that either one is a hydrogen atom or the other is a contiguous group. The substitution positions of R3 and R4 are not particularly limited, and any one is a nitrogen atom and the other is a material. Coco is preferably substituted for: one of the two carbon atoms constituting the side of the benzene (four) saliva and the benzimizac lQpyHd_) ring which is not adjacent to the nitrogen atom. It is to be noted that the compound represented by the above formula (1) of the present invention can be used in the form of a substitution position including ... and r4 15 201237111

之至少兩種位置異構物之混合物D 上述式（1 )中，R1〜R4之較佳組合可舉例如下述組合： R1為（C1〜C4)烷基或苯基（以（C1〜C4)烷基為佳，以曱基較佳），R為氰基或胺甲醯基（以氰基為佳）；R3為氫原子、曱基'、曱氧基（以甲氧基為佳）；R4為磺基。上述式（1)中，R5中，（C1〜C4)烷硫基可舉例如：烷基部分為直鏈或支鏈之無取代（C1〜C4)烷硫基，以直鏈為佳。具體例可舉例如：甲硫基、乙硫基、正丙硫基、正丁硫基等直鏈（C1〜C4)烷硫基；異丙硫基、異丁硫基、二級丁硫基、三級丁硫基等支鏈（C1〜C4)烷硫基等。 R中’經從由經基、確基及缓基所構成之群組中選出之至少一種基所取代之（C1〜C4)烷硫基可舉例如：在（C1 〜C4)烷硫基之任意碳原子上具有此等取代基者。該取代基的數目通常為1或2個，以1個為佳。取代基的位置係無特別限制’較佳是取代在：烷硫基之硫原子所鍵結之碳原子以外之碳原子。具體例可舉例如：2-羥基乙硫基、2-羥基丙硫基、3-經基丙硫基等羥基（C1〜C4)烷硫基；2_磺基乙硫基、3_磺基丙硫基等磺基（C1〜C4)烷硫基；2-羧基乙硫基、3-羧基丙硫基、4-羧基丁硫基等羧基（C1〜C4)烷硫基等。上述中’較佳的R5可舉例如：磺基（C1〜C4)烷硫基或羧基（C1〜C4)烷硫基，以磺基（Ci〜^4)烷硫基較佳，以磺基丙硫基特佳。上述式（1)中，R6中，（C1〜C4)烷基羰基胺基可舉例 16 201237111 如：烷基部分為直鏈或支鏈之無取代（Cl〜C4)烷基羰基胺基，以直鏈為佳。具體例可舉例如：乙醯基胺基（甲基羰基胺基）、丙醯基胺基（乙基羰基胺基）、正丙基羰基胺基、正丁基羰基胺基等直鏈（C1〜C4)烷基羰基胺基；異丙基羰基胺基、異丁基羰基胺基、二級丁基羰基胺基、三甲基乙醯基胺基（三級丁基羰基胺基）等支鏈（C1〜C4)烷基羰基胺基等。此等中’以直鏈（C1〜C4)烷基羰基胺基為佳，以乙醯基胺基特佳。 R5及R6之較佳組合為：R5為磺基（C1〜C4)烷硫基、 R6為乙醯基胺基之組合’以R5為磺基丙硫基、R6為乙醯基胺基之組合特佳。上述式（1)中’ R7中，（C1〜C4)烷硫基可舉例如：烷基部分為直鏈或支鏈之無取代（C1〜C4)烷硫基，以直鏈為佳。具體例可舉例如：曱硫基、乙硫基、正丙硫基、正丁硫基等直鏈（C1〜C4)烷硫基；異丙硫基、異丁硫基、二級丁硫基、三級丁硫基等支鏈（C1〜C4)烷硫基等。The mixture of at least two positional isomers D. In the above formula (1), a preferred combination of R1 to R4 is, for example, the following combination: R1 is (C1 to C4) alkyl or phenyl (by (C1 to C4) Preferably, an alkyl group is preferably a fluorenyl group, R is a cyano group or an amine carbaryl group (preferably a cyano group); and R3 is a hydrogen atom, a fluorenyl group, and a decyloxy group (preferably a methoxy group); R4 is a sulfo group. In the above formula (1), the (C1 to C4) alkylthio group in R5 may, for example, be an unsubstituted (C1-C4) alkylthio group in which the alkyl moiety is linear or branched, and a linear chain is preferred. Specific examples thereof include a linear (C1 to C4) alkylthio group such as a methylthio group, an ethylthio group, a n-propylthio group or a n-butylthio group; an isopropylthio group, an isobutylthio group, and a secondary butylthio group; A branched (C1 to C4) alkylthio group such as a tertiary butylthio group. The (C1 to C4) alkylthio group substituted by at least one selected from the group consisting of a trans group, a determinent group and a slow group in R may, for example, be a (C1 to C4) alkylthio group. Those having such substituents on any carbon atom. The number of the substituents is usually 1 or 2, preferably 1 or more. The position of the substituent is not particularly limited. It is preferred to substitute a carbon atom other than the carbon atom to which the sulfur atom of the alkylthio group is bonded. Specific examples thereof include a hydroxyl group (C1 to C4) alkylthio group such as 2-hydroxyethylthio group, 2-hydroxypropylthio group or 3-propylpropylthio group; 2-sulfoethylthio group and 3-sulfo group. a sulfo (C1 to C4) alkylthio group such as a propylthio group; a carboxyl group (C1 to C4) alkylthio group such as a 2-carboxyethylthio group, a 3-carboxypropylthio group or a 4-carboxybutylthio group; The above preferred 'R5' may, for example, be a sulfo (C1 to C4) alkylthio group or a carboxyl group (C1 to C4) alkylthio group, preferably a sulfo group (Ci~^4) alkylthio group, and a sulfo group. Propylthio is preferred. In the above formula (1), in R6, the (C1 to C4) alkylcarbonylamino group can be exemplified by 16 201237111, such as: the alkyl moiety is a linear or branched unsubstituted (Cl~C4) alkylcarbonylamino group, Straight chain is preferred. Specific examples thereof include a straight chain (C1) such as an acetamino group (methylcarbonylamino group), a propyl fluorenyl group (ethylcarbonylamino group), a n-propylcarbonylamino group or a n-butylcarbonylamino group. ~C4) alkylcarbonylamino group; isopropylcarbonylamino group, isobutylcarbonylamino group, secondary butylcarbonylamino group, trimethylethylamino group (tertiary butylcarbonylamino group) A chain (C1 to C4) alkylcarbonylamino group or the like. Among these, 'the linear (C1~C4) alkylcarbonylamino group is preferred, and the ethylamino group is particularly preferred. A preferred combination of R5 and R6 is: a combination of R5 is a sulfo group (C1 to C4) alkylthio group, and R6 is an ethylamino group. A combination of R5 is a sulfopropylthio group and R6 is an ethylamino group. Very good. In the above formula (1), the (C1 to C4) alkylthio group in the formula (1) may, for example, be an unsubstituted (C1-C4) alkylthio group in which the alkyl moiety is linear or branched, and a straight chain is preferred. Specific examples thereof include a linear (C1 to C4) alkylthio group such as an anthracenylthio group, an ethylthio group, a n-propylthio group or a n-butylthio group; an isopropylthio group, an isobutylthio group, and a secondary butylthio group; A branched (C1 to C4) alkylthio group such as a tertiary butylthio group.

7 I 中丄從由經基 '續基及缓基所構成之群組中選出之至少一種基所取代之（C1〜C4)烷硫基可舉例如：在〜C4)燒硫基之任意碳原子上具有此等取代基者。該取代基的數目通常為1或2個’以1個為佳。取代基的位置係無特別限制’較佳是取代在：烷硫基之硫原子所鍵結子以外之碳原子。 —具體例可舉例如：2·經基乙硫基、2-經基丙硫基、3_ ^基丙硫基等經基（C1〜C4)院硫基；2·續基乙硫基、3_續 17 201237111 基丙硫基等磺基（Cl〜C4)烷硫基；2-羧基乙硫基、3-羧基丙硫基、4-羧基丁硫基等羧基（ci〜C4)烷硫基等。上述中，較佳的R7可舉例如：磺基（C 1〜C4)烷硫基或羧基（C1〜C4)烷硫基’以磺基（C1〜C4)烷硫基較佳，以項基丙基硫基特佳。上述式（1)中’ R8中’（Cl〜C4)烷基羰基胺基可舉例如：烧基部分為直鏈或支鏈之無取代（C1〜C4)烷基羰基胺基，以直鏈為佳。具體例可舉例如：乙醯基胺基（曱基羰基胺基）、丙酿基胺基（乙基羰基胺基）、正丙基羰基胺基、正丁基缓基胺基等直鏈（C1〜C4)烷基羰基胺基；異丙基羰基胺基、異丁基羰基胺基、二級丁基羰基胺基、三甲基乙醯基胺基（三級丁基羰基胺基）等支鏈（C1〜C4)烷基羰基胺基等。此等中’以直鏈（C1〜C4)烷基羰基胺基為佳，以乙醯基胺基特佳。 R7及R8之較佳組合為：R7為磺基（C1〜C4)烷硫基、 R8為乙醯基胺基之組合，以R7為磺基丙硫基、R8為乙醯基胺基之組合特佳。上述式（1)中，R9及Ri〇中，（CI〜C4)烷基可舉例如：包含為佳者等在内’均與上i R1巾之（C1〜C4)烧基相同者。及R中，（C1〜C4)烷氧基可舉例如：包含為佳者等在内均與。上述中之（C1〜C4)烧氧基相同者。 R及R中，經從由羥基、（c 1〜C4)烷氧基、磺基及叛基所構成之群組中選出之至少—種基所取代之（C1〜C4) 201237111 烷氧基可舉例如：在（C1〜C4)烷氧基之任意碳原子上具有此等取代基者。該取代基的數目通常為1& 2個，以i個 • 為佳。取代基的位置係無特別限制，較佳是取代在：烷氧 ^ 基之氧原子所鍵結之碳原子以外之碳原子。具體例可舉例如：2_羥基乙氧基、2_羥基丙氧基、3_ 經基丙氧基等經基（C1〜C4)烷氧基；2_磺基乙氧基、3_磺基丙氧基4_硕基丁氧基等磺基（C1〜C4)烷氧基；2-羧基乙氧基、3-羧基丙氧基、4_羧基丁氧基等羧基（ci〜c4)烷氧基等。上述中，較佳的R9可舉例如：磺基（C1〜C4)烷氧基及羧基（C1〜C4)烷氧基，以磺基（C1〜C4)烷氧基較佳，以磺基丙氧基、磺基丁氧基特佳。上述令，較佳的R10可舉例如：（C1〜C4)烧基、〜 C4)烷氧基、磺基（C1〜C4)烷氧基、羧基（ci〜c4)烷氧基、乙醯基胺基，以（C1〜C4)烷基較佳，以甲基特佳。 I。R9及R10之較佳組合為：R9為磺基（C1〜C4)烷氧基、 R為（C1〜C4)烷基之組合，以R9為磺基丙氧基（特別以3_ 續基丙氧基為佳）H甲基之組合；和r9為續基丁氧基 (特別以4-磺基丁氧基為佳）、Ri〇為甲基之組合特佳。土上述式（1)中，RH〜R13中，（C1〜C4)烷基可舉例如：包含為佳者等在内，均與上述R1中之（C1〜C4)燒基相同者。 ^ R〜R 3中’（C1〜C4)烷氧基可舉例如：包含為佳者等在内，均與上述r3及r4中之（ci〜C4)烷氧基相同者。 19 201237111 R〜R中，經從由羥基、（Cl〜C4)烷氧基、磺基及羧基所構成之群組中選出之至少一種基所取代之（c丨〜C4) , 烷氧基可舉例如：包含為佳者等在内，均與上述R5及R6 v 中之經從由羥基、（C1〜C4)烷氧基、磺基及羧基所構成之群組中選出之至少一種基所取代之（c】〜C4)烷氧基相同者。 R11〜R13中，（C1〜C4)烷磺醯基可舉例如：直鏈或支鏈之（C1〜C4)烷磺醯基，以直鏈為佳。具體例可舉例如：甲％醯基、乙磺醯基、正丙磺醯基、正丁磺醯基等直鏈（Cl 〜C4)烷磺醯基；異丙磺醯基、異丁磺醯基等支鏈（C1〜c4) 烷磺醯基等。上述中，以曱磺醯基、乙磺醯基、異丙磺醯基為佳，以曱磺醯基特佳。 R R中’經攸由經基、續基及叛基所構成之群組中選出之至少一種基所取代之（C1〜C4)烷磺醯基可舉例如：在上述（C1〜C4)烷磺醯基之任意碳原子上取代有上述基者。該取代基的數目通常為丨或2個，以丨個為佳。取代基的位置係無特別限制。具體例可舉例如：羥基乙磺醯基、2_羥基丙磺醯基等羥基取代（C1〜C4)烷磺醯基；2_磺基乙磺醯基、3_磺基丙 . 磺醯基等磺基取代（C1〜C4)烷磺醯基；2_羧基乙磺醯基、 3-幾基丙磺醯基等羧基取代（ci〜C4)烷磺醯基等。上述中，較佳的R11可舉例如：氫原子、羧基、磺基、硝基、氯原子、曱基、曱氧基、（C1〜C4)烷磺醯基，以氫 20 201237111 原子；作為拉電子性取代基之羧基、磺基、硝基、氣原子、 (C 1〜C4)烷磺醯基；或甲基、甲氧基較佳，以氫原子、氣原子特佳。上述中，較佳的R12可舉例如：氫原子、羧基、磺基、硝基、氯原子、甲基、甲氧基、胺磺醯基、（C1〜C4)烷磺醯基、羧基（C1〜C4)烷磺醯基、磺基（C1〜C4)烷磺醯基，以氫原子；作為拉電子性取代基之羧基、磺基、硝基、氯原子、胺磺醯基、（C1〜C4)烷磺醯基、羧基（C1〜C4)烷磺醯基、磺基（C1〜C4)烷磺醯基；或甲基、甲氧基為佳，以磺基、硝基、甲基、甲氧基、胺磺醯基、磺基丙磺醯基、羧基乙續醯基較佳，以續基特佳。上述中，較佳的R13可舉例如：氫原子、羧基、磺基、甲氧基、硝基、氣原子、（C1〜C4)烷磺醯基，以氫原子；作為拉電子性取代基之羧基、磺基、硝基、氣原子、（ci 〜C4)烧續醯基；或甲氧基為佳，以氫原子特佳。 R11〜R13之較佳組合為：r"為氫原子、為磺基、 R13為氫原子之組合；R11為氫原子、Ri2為胺磺醯基、rU 為氫原子之組合；或r11為氫原子、為氯原子、r!3為 %基之組合，以R11為氫原子、R»2為氣原子、RU為磺基之組合特佳。以上述式（1)中之各種取代基、其組合、及其取代位置等中所記載之為佳者彼此組合而成之化合物較佳，以較佳者彼此組合而成之化合物更佳。更佳者彼此組合、為佳者與較佳者組合等亦相同。 21 201237111 上述式（1)中，較佳組合之具體例可舉例如下述⑴〜（^) 之組合。相較於（i) ’以（ii)為佳，以（iii)最佳。 1 ⑴ m 下述組合： R1為曱基或苯基， R2為氰基或胺甲醯基， R3為氫原子；甲基；或甲氧基， R4為磺基， R5為經磺基或羧基所取代之（C1〜C4)烷硫基， R6為（C1〜C4)烷基羰基胺基， R7為經磺基或羧基所取代之（C1〜C4)烷硫基， R8為（C1〜C4)烷基羰基胺基， R9為磺基（C1〜C4)烷氧基， R1Q為（C1〜C4)烷基或乙醯基胺基， R11〜R13分別獨立地為：氫原子；羧基；磺基；甲基；曱氧基，氯原子；.ί肖基；胺續酿基；或是經橫基或缓基所取代之（C1〜C4)烷磺醯基。 (Η) 下述組合： ^ R1為曱基，、 r2為氰基或胺甲醯基， r3為氫原子；甲基；或甲氧基， R為續基， R為項基（C1〜C4)烧硫基’ 22 201237111 R6為（Cl〜C4)烷基羰基胺基， R7為磺基（Cl〜C4)烷硫基， R8為（C1〜C4)烷基羰基胺基， * R9為磺基（C1〜C4)烷氧基，響磺基；曱基；甲氣 R〇為（C1〜C4)烧基或乙醯基胺基， R11〜R13分別獨立地為：氫原子；基；氣原子；硝基；或胺磺醯基。 (iii) 下述組合： R1為甲基， R2為氰基， R3為氫原子或曱氧基， R4為磺基， R5為磺基（C1〜C4)烷硫基， R為乙酿基胺基， R7為磺基（C1〜C4)烷硫基， R8為乙醯基胺基， R9為磺基丙氧基或磺基丁氧基， R10為（C1〜C4)烷基， r11為氫原子或磺基， r12為磺基或氣原子， R13為氫原子或磺基。以例如如下所述& 之結構式係以游離上述式（1)所示之偶氮化合物能夠方法來合成。此外，各步驟中之化合物 23 201237111 酸之形態來表示。再者，在下述式（7)〜（14)中，Rl〜Rl3係表示與上述式 (1)中之RkW3相同的意義。藉由慣用方法來使下述式（7)所示之化合物進行重氮化後，藉由慣用方法來使所得之重氮化合物與下述式（8)所示之化合物進行耦合反應，而獲得下述式（9)所示之化合物。 ⑺ ⑻ ♦ R13 R5The (C1 to C4) alkylthio group substituted with at least one group selected from the group consisting of a group consisting of a contiguous group and a slow group may, for example, be any carbon which is sulfur-burned at ~C4) Those with such substituents on the atom. The number of such substituents is usually 1 or 2', preferably 1 or more. The position of the substituent is not particularly limited. It is preferred to substitute a carbon atom other than the bond of the sulfur atom of the alkylthio group. - Specific examples include, for example, 2: mercaptothio group, 2-propylpropylthio group, 3-methylpropylthio group, and the like (C1 to C4), a thiol group; 2. a contigyl ethylthio group, 3 _Continued 17 201237111 Sulfo (Cl~C4) alkylthio group such as propyl propylthio; carboxyl group (ci~C4) alkylthio group such as 2-carboxyethylthio, 3-carboxypropylthio, 4-carboxybutylthio Wait. In the above, preferred R7 may, for example, be a sulfo group (C 1 - C4) alkylthio group or a carboxyl group (C1 to C4) alkylthio group, preferably a sulfo group (C1 to C4) alkylthio group. Propylthio is preferred. In the above formula (1), the 'R8' (Cl~C4) alkylcarbonylamino group may, for example, be a linear or branched unsubstituted (C1-C4) alkylcarbonylamino group, which is a straight chain or a branched chain. It is better. Specific examples thereof include a straight chain such as an acetamino group (mercaptocarbonylamino group), a propylamino group (ethylcarbonylamino group), a n-propylcarbonylamino group, or a n-butyl sulfhydryl group ( C1 to C4) alkylcarbonylamino group; isopropylcarbonylamino group, isobutylcarbonylamino group, secondary butylcarbonylamino group, trimethylethylamino group (tertiary butylcarbonylamino group), etc. Branched (C1 to C4) alkylcarbonylamino group and the like. Among these, 'the linear (C1~C4) alkylcarbonylamino group is preferred, and the ethylamino group is particularly preferred. A preferred combination of R7 and R8 is a combination of R7 is a sulfo(C1~C4)alkylthio group, R8 is an ethylamino group, and R7 is a sulfopropylthio group and R8 is an ethylamino group. Very good. In the above formula (1), in the case of R9 and Ri(R), the (CI~C4) alkyl group may be, for example, the same as those of the (C1 to C4) alkyl group of the upper i R1 towel. In the case of R, the (C1 to C4) alkoxy group may be, for example, a good one or the like. The above (C1 to C4) alkoxy groups are the same. And R and R are substituted by at least one selected from the group consisting of a hydroxyl group, a (c 1~C4) alkoxy group, a sulfo group and a thiol group (C1 to C4) 201237111 alkoxy group For example, those having such a substituent on any carbon atom of the (C1 to C4) alkoxy group. The number of such substituents is usually 1 & 2, preferably i. The position of the substituent is not particularly limited, and it is preferred to substitute a carbon atom other than the carbon atom to which the oxygen atom of the alkoxy group is bonded. Specific examples thereof include a (C1 to C4) alkoxy group such as a 2-hydroxyethoxy group, a 2-hydroxypropyloxy group, a 3-hydroxypropoxy group, and the like; a 2-sulfoethoxy group, a 3-sulfo group. a sulfo(C1~C4) alkoxy group such as a propoxy group 4_alkylbutoxy group; a carboxyl group (ci~c4) alkane such as a 2-carboxyethoxy group, a 3-carboxypropoxy group or a 4-carboxybutoxy group; Oxyl and the like. In the above, preferred R9 may, for example, be a sulfo (C1 to C4) alkoxy group or a carboxyl group (C1 to C4) alkoxy group, preferably a sulfo group (C1 to C4) alkoxy group, and a sulfopropyl group. The oxy group and the sulfobutoxy group are particularly preferred. In the above-mentioned order, preferred R10 may, for example, be a (C1 to C4) alkyl group, a C4) alkoxy group, a sulfo group (C1 to C4) alkoxy group, a carboxyl group (ci~c4) alkoxy group or an ethyl group. The amine group is preferably a (C1 to C4) alkyl group, and particularly preferably a methyl group. I. A preferred combination of R9 and R10 is: R9 is a sulfo(C1~C4)alkoxy group, R is a combination of (C1~C4)alkyl groups, and R9 is a sulfopropoxy group (especially 3_ contigyl propyloxy) The group is preferably a combination of H methyl groups; and r9 is a combination of a decyloxy group (particularly 4-sulfobutoxy group) and a combination of Ri 〇 methyl groups. In the above formula (1), in the case of RH to R13, the (C1 to C4) alkyl group may be, for example, the same as those of the (C1 to C4) alkyl group in the above R1. The R (R1 to C4) alkoxy group in R to R 3 may be, for example, the same as the (ci~C4) alkoxy group in the above r3 and r4. 19 201237111 R to R, substituted by at least one group selected from the group consisting of a hydroxyl group, a (Cl~C4) alkoxy group, a sulfo group and a carboxyl group (c丨~C4), the alkoxy group may be For example, at least one selected from the group consisting of a hydroxyl group, a (C1 to C4) alkoxy group, a sulfo group and a carboxyl group in the above R5 and R6 v, including the preferred ones, etc. Substituting (c) to C4) alkoxy is the same. Among R11 to R13, the (C1 to C4) alkanesulfonyl group may, for example, be a linear or branched (C1 to C4) alkanesulfonyl group, preferably a straight chain. Specific examples thereof include a straight chain (Cl ～ C 4 ) alkanesulfonyl group such as a methyl sulfhydryl group, an ethyl sulfonyl group, a n-propyl sulfonyl group or a n-butyl sulfonyl group; an isopropyl sulfonyl group and an isobutyl sulfonium group; Branches such as bases (C1 to c4), alkanesulfonyl groups, and the like. Among the above, it is preferably a sulfonyl group, an ethylsulfonyl group or an isopropylsulfonyl group, and is preferably a sulfonyl group. The (C1 to C4) alkanesulfonyl group substituted by at least one selected from the group consisting of a thiol group, a contiguous group and a ruthenium group in the RR can be, for example, the above (C1 to C4) alkane sulfonate. The above base is substituted on any carbon atom of the fluorenyl group. The number of the substituents is usually 丨 or 2, preferably one. The position of the substituent is not particularly limited. Specific examples thereof include a hydroxy-substituted (C1 to C4) alkanesulfonyl group such as a hydroxyethanesulfonyl group or a 2-hydroxypropanesulfonyl group; a 2-sulfoethylsulfonyl group; a 3-sulfopropyl group; a sulfonyl group; The sulfo group is substituted with a (C1 to C4) alkanesulfonyl group; a carboxyl group such as a 2-carboxycarbonylsulfonyl group or a 3-methylpropanesulfonyl group (ci~C4) alkanesulfonyl group. In the above, preferred R11 may, for example, be a hydrogen atom, a carboxyl group, a sulfo group, a nitro group, a chlorine atom, a decyl group, a decyloxy group or a (C1 to C4) alkanesulfonyl group, and a hydrogen atom of 20, 2012,711, 11 atom; The carboxyl group, the sulfo group, the nitro group, the gas atom or the (C 1 to C4) alkanesulfonyl group of the electronic substituent; or the methyl group or the methoxy group is preferred, and a hydrogen atom or a gas atom is particularly preferred. In the above, preferred R12 may, for example, be a hydrogen atom, a carboxyl group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group, an amidoxime group, a (C1 to C4) alkanesulfonyl group or a carboxyl group (C1). ~C4) alkanesulfonyl, sulfo (C1~C4) alkanesulfonyl, a hydrogen atom; a carboxyl group as a chargeable substituent, a sulfo group, a nitro group, a chlorine atom, an amine sulfonyl group, (C1~) C4) alkanesulfonyl, carboxyl (C1 to C4) alkanesulfonyl, sulfo (C1 to C4) alkanesulfonyl; or methyl, methoxy is preferred, sulfo, nitro, methyl, The methoxy group, the amine sulfonyl group, the sulfopropyl sulfonyl group, and the carboxy group are preferably the same. In the above, preferred R13 may, for example, be a hydrogen atom, a carboxyl group, a sulfo group, a methoxy group, a nitro group, a gas atom or a (C1 to C4) alkanesulfonyl group, a hydrogen atom; and an electron-donating substituent; A carboxyl group, a sulfo group, a nitro group, a gas atom, or a (ci~C4) group is preferably a methoxy group, and a hydrogen atom is particularly preferred. A preferred combination of R11 to R13 is: r" is a hydrogen atom, a sulfo group, and R13 is a combination of hydrogen atoms; R11 is a hydrogen atom, Ri2 is an aminesulfonyl group, and rU is a combination of hydrogen atoms; or r11 is a hydrogen atom. The combination of a chlorine atom and r!3 as a % group is particularly preferable in that R11 is a hydrogen atom, R»2 is a gas atom, and RU is a sulfo group. The compound which is preferably combined with each other as described in the above formula (1), the combination thereof, and the position of substitution thereof is preferably a compound which is preferably combined with each other. The better, the better, the better, the better, the better. 21 201237111 In the above formula (1), a specific example of the preferable combination is, for example, a combination of the following (1) to (^). (ii) is preferred to (ii) and (iii) is preferred. 1 (1) m The following combination: R1 is a fluorenyl group or a phenyl group, R2 is a cyano group or an aminomethyl group, R3 is a hydrogen atom; a methyl group; or a methoxy group, R4 is a sulfo group, and R5 is a sulfo group or a carboxyl group. Substituted (C1~C4) alkylthio group, R6 is (C1~C4)alkylcarbonylamino group, R7 is (C1~C4)alkylthio group substituted by sulfo group or carboxyl group, and R8 is (C1~C4) An alkylcarbonylamino group, R9 is a sulfo (C1~C4) alkoxy group, R1Q is a (C1~C4) alkyl group or an ethylamino group, and R11 to R13 are each independently: a hydrogen atom; a carboxyl group; a group; a methyl group; a methoxy group; a chlorine atom; a succinyl group; an amine aryl group; or a (C1 to C4) alkanesulfonyl group substituted by a transverse or a slow group. (Η) The following combination: ^ R1 is a fluorenyl group, r2 is a cyano group or an amine carbaryl group, r3 is a hydrogen atom; a methyl group; or a methoxy group, R is a hydrazine group, and R is a term group (C1 to C4) ) sulfur-based '22 201237111 R6 is (Cl~C4) alkylcarbonylamino group, R7 is sulfo (Cl~C4) alkylthio group, R8 is (C1~C4)alkylcarbonylamino group, *R9 is sulfonate a (C1~C4) alkoxy group, a sulfo group; a fluorenyl group; a gas R 〇 is a (C1~C4) alkyl group or an acetamino group, and R11 to R13 are each independently: a hydrogen atom; a base; Atom; nitro; or amine sulfonyl. (iii) The following combination: R1 is a methyl group, R2 is a cyano group, R3 is a hydrogen atom or a decyloxy group, R4 is a sulfo group, R5 is a sulfo group (C1 to C4) alkylthio group, and R is an ethyl aryl amine. a group, R7 is a sulfo (C1 to C4) alkylthio group, R8 is an ethylamino group, R9 is a sulfopropoxy group or a sulfobutoxy group, R10 is a (C1 to C4) alkyl group, and r11 is a hydrogen group. An atom or a sulfo group, r12 is a sulfo group or a gas atom, and R13 is a hydrogen atom or a sulfo group. The azo compound represented by the above formula (1) can be synthesized, for example, by the following formula & Further, the form of the compound 23 201237111 in each step is represented by the form of the acid. In the following formulas (7) to (14), R1 to Rl3 have the same meanings as RkW3 in the above formula (1). After the compound represented by the following formula (7) is diazotized by a conventional method, the obtained diazo compound is subjected to a coupling reaction with a compound represented by the following formula (8) by a conventional method. A compound represented by the following formula (9). (7) (8) ♦ R13 R5

-NH, 卟 Re ⑼ 藉由慣用方法來使所得之上述式(9)所示之化合物進行重氣化後’冑由慣用方法來使所得之重氣化合物血下述式⑽所示之化合物進㈣合反應，而獲得下述式⑴）所系之化合物。-NH, 卟Re (9) By subjecting the obtained compound represented by the above formula (9) to gasification by a conventional method, the compound of the following formula (10) is obtained by a conventional method. (4) The reaction is carried out to obtain a compound of the following formula (1)).

π αυ 藉由慣用方法來使所得之上述式⑴）所示之化人來行重氣化後，藉由慣用方法來使所得之重敗化合物二 201237111 式（12)所示之化合物進件，成…日仃輕合反應’而獲付下述式（13)所示之化合物。π αυ is obtained by a conventional method, and the obtained compound represented by the above formula (1)) is subjected to gasification, and the obtained compound of the formula (12) is obtained by a conventional method. A compound represented by the following formula (13) is obtained as a "light-synthesis reaction".

(13) /精由慣用方法來使所得之上述式（13)所示之化合物進仃重氮化後，藉由慣用方法來使所得之重氮化合物與下述式（14)所示之化合物進行耦合反應，藉此能夠獲得上述式（1) 所示之偶氮化合物。(13) / After diluting the obtained compound represented by the above formula (13) by a conventional method, the obtained diazo compound and a compound represented by the following formula (14) are obtained by a conventional method. The coupling reaction is carried out, whereby the azo compound represented by the above formula (1) can be obtained.

R3 再者’上述式（14)所示之化合物能夠依據專利文獻6 中所記載之方法合成。上述式（1)所示之偶氮化合物之較佳具體例係並無特別限定，可與_ J舉例如：下述表1〜].6中所列舉之結構式所示之化合物等。在各表中’為了方便，磺基、羧基等官能基係以游離酸之形態來記栽。 25 201237111 [表l] 化合物編號結構式 ⑴-1 5〇3h so3h so3h ClN=N一~N=N——N=N-—N=N-《^)=rN ho3s^ achn~*^ achn^ h3c ho ^so3h (1)-2 so3h so3h so3h Cl~~N=N——N=N——N=N——N=N— H03S^ AcHN^ AcHN^ H3c^ HO v|^y^H3 ho3s ⑴-3 so3h so3h _^o3h C)~~^~V-N=N-~^^^N=N^-^~^~N=N^-^~^—N=N~~^/^n ho3s^ AcHN^ AcHN^ h3c~^ ho Y^Ych：> ho3s-^^ ⑴-4 S03H j03H S03H s-^ /s"^ ^0_^3CV-/cn Cl—N=N—一N=N— HOzS~^ AcHN AcHN~ HjC^ HO^VS) h3c"\^ so3h ⑴-5 so3h so3h so3h P~^ P^*CwCN Cl-N=N-*—M=N——N-N——N=N— H03S^ AcHN AcHN广 H3C HO h3cX^A'so3h ⑴-6 jS〇aH .so3h so3h p-' r-P~r^^yJ,^ Cl—N=N—·~N=N——N=N——N=N— H03S严 AcHN NMn H3C^ W<f V^SOjH Η3〇·^ν^ 26 201237111 [表2] 化合物編號结構式 ⑴-7 so3h so3h so3h β-/ p-^HaC CN C1—N=N—"N=N——N=N——N=N—^^\==|sj H03S； AcHN^ AcHN h3c HO S^so3h och3 (1)-8 so3h so3h jso3h C!^N=N——N=N——N=N--^^—N=N-^^\r|s| ho3s^ achu achn~ h3c~ m vS h3co ⑴-9 so3h so3h jso3h Cl—'^~V-N=N——N=N——N=N—<λ~^—N=N— H02S AcHN AcHNI H3C； HO NV^S〇3H H3CO ⑴-10 S03H SOjH βΟζΗ P^~H3C\Pu Cl*-^~~^-N=N--^~^~~N=N——N=N——N=N— H03S广 AcHN AcHN H3C~ HC> V'S 'OCHj so3h (1)-11 ^o3h so3h so3h ^，」"""^，」"""^O^HaC CN Cl~N=N—^_jj~N=N"™~N=N™^^—N=N-\^Vrfsj H03S^ AcHN^ AcHN^ h;jc ho^ vS ho3sa^〇ch3 (1)-12 so3h so3h 」so3h P~^ _P^H3CV-(pN ct—V-N=N—~^N~C"^—N=N—^~^~-N=N-^""V=rN H〇/^Ac^/ A^T η}~^ 、\)CH3 27 201237111 [表3]R3 Further, the compound represented by the above formula (14) can be synthesized in accordance with the method described in Patent Document 6. The preferred embodiment of the azo compound represented by the above formula (1) is not particularly limited, and examples thereof include a compound represented by the structural formulas listed in the following Tables 1 to 6. In each of the tables, the functional groups such as a sulfo group and a carboxyl group are recorded in the form of a free acid for convenience. 25 201237111 [Table l] Compound number structure formula (1)-1 5〇3h so3h so3h ClN=N_~N=N——N=N-—N=N-“^)=rN ho3s^ achn~*^ achn^ H3c ho ^so3h (1)-2 so3h so3h so3h Cl~~N=N——N=N——N=N——N=N— H03S^ AcHN^ AcHN^ H3c^ HO v|^y^H3 ho3s (1)-3 so3h so3h _^o3h C)~~^~VN=N-~^^^N=N^-^~^~N=N^-^~^-N=N~~^/^n ho3s ^ AcHN^ AcHN^ h3c~^ ho Y^Ych:> ho3s-^^ (1)-4 S03H j03H S03H s-^ /s"^ ^0_^3CV-/cn Cl—N=N—one N=N— HOZS~^ AcHN AcHN~ HjC^ HO^VS) h3c"\^ so3h (1)-5 so3h so3h so3h P~^ P^*CwCN Cl-N=N-*-M=N——NN——N=N— H03S^ AcHN AcHN wide H3C HO h3cX^A'so3h (1)-6 jS〇aH .so3h so3h p-' rP~r^^yJ,^ Cl—N=N—·~N=N——N=N—— N=N—H03S YanAcHN NMn H3C^ W<f V^SOjH Η3〇·^ν^ 26 201237111 [Table 2] Compound number structure formula (1)-7 so3h so3h so3h β-/ p-^HaC CN C1—N= N—"N=N——N=N——N=N—^^\==|sj H03S; AcHN^ AcHN h3c HO S^so3h och3 (1)-8 so3h so3h jso3h C!^N=N ——N=N——N=N--^^—N=N-^^\r|s| ho3s^ achu achn~ h3c~ m vS h3co (1)-9 so3h so3h jso 3h Cl—'^~VN=N——N=N——N=N—<λ~^—N=N—H02S AcHN AcHNI H3C; HO NV^S〇3H H3CO (1)-10 S03H SOjH βΟζΗ P^ ~H3C\Pu Cl*-^~~^-N=N--^~^~~N=N——N=N——N=N—H03S Wide AcHN AcHN H3C~ HC> V'S 'OCHj so3h (1 )-11 ^o3h so3h so3h ^,""""^,""""^O^HaC CN Cl~N=N-^_jj~N=N"TM~N=NTM^ ^—N=N-\^Vrfsj H03S^ AcHN^ AcHN^ h;jc ho^ vS ho3sa^〇ch3 (1)-12 so3h so3h ”so3h P~^ _P^H3CV-(pN ct—VN=N—~ ^N~C"^—N=N—^~^~-N=N-^""V=rN H〇/^Ac^/ A^T η}~^ ,\)CH3 27 201237111 [Table 3]

化合物編號結搆弍 (1)-13 so3h so3h ^^so3h s-^ O^H3C CN Cl—N=N一—N=N—N=N—^~^—Ν=Ν--4^)^γν HOjS^ AcHN尸 AcHN〆 H3C HO~ (1)-14 so3h so3h /-so3h s-^ 〇-^H3C CN Cl—^~^—N=N—~N=N-—N=N-—N=N— HOjS^ AcHN^ AcHN^ H30^ H0^~ V^yCH3 ho3s (1)-15 so3h so3ih /-so3h Cl~~N=N——N=N—N=N"^^)=tj H03S^ AcHN^ AcHN H3C Hd^~ ho3s^^ (1)-16 so3h so3h ^so3h Cl—N=N—C~^—N=N——N=N""C~>y—N=N— H03S^ AcHH AcHU h3c ho7" yS h3c#J^ so3h (1)-17 S03H S03H /T-S03H /^CWCN Cl—N=N——N=N——Ν=Ν-^λ~^—N=N-^ %：n Ho}^ AC^T h/^ H>V, (1)-18 so3h so3h ^^so3h js-7^ ^^^3S_/cn Cl—N=N—~N=N——N=N—^~^—N=N— H03S》"~^ AgHN尸 AcHN H2Q HC» Y^YS0^H h3〇-M 28 201237111 [表4] 化合物編號結構式 (1)-19 sd3h so3h so3h ^°^^3Cy_/CN H03S^ AcHN^ AcHhi H3C； ΗΟ^~ V^) ^so3h (D-20 S03H μ〇ζΗ S03H J/-<0」H3V<cn ChH^-N=N—N=N—N=N-^>-N=N-^^ HOjS~^ AcHN广 AcHt/~ 卜13。广 HO y\ y ho3s (1)-21 S03H ,S03H r-S02H JS-^ _/°"^Cv_J：N Cl一/~~y~N=N—~—N=N——N=N〜^""^—N=N—^^=|s| H03sT AcHN AcHN h3c HO HOaS (1)-22 so3h so3h ^^so3h s-^ o-^3ccn Ci—N=N——*N=N一'—N=N——N=N— HOzS AcHN AcHH H3C^ ΗΟ~ YK ^^so3h (1)-23 so3h so3h so3h 』 ^^^3CwCN CH^y-N=N一—N=N——N=N——N=N—4^~Vs：n HOaS^ AcHN^ AcHN厂 H3C 厂 HO yS 、S〇3H (1)-24 5〇3H yS03H S03H Cl s-7^ __/3-/Γ^3〇\_/：Ν Cl^y-N=N——N=N—^~~^~N=N—^~^—N=N— H03s~^ AcHN厂 AcHN H3C^ HO^ ho3s 29 201237111 [表5]Compound number structure 弍(1)-13 so3h so3h ^^so3h s-^ O^H3C CN Cl—N=N—N=N—N=N—^~^—Ν=Ν--4^)^γν HOjS^ AcHN corpse AcHN〆H3C HO~ (1)-14 so3h so3h /-so3h s-^ 〇-^H3C CN Cl-^~^-N=N-~N=N--N=N--N= N— HOjS^ AcHN^ AcHN^ H30^ H0^~ V^yCH3 ho3s (1)-15 so3h so3ih /-so3h Cl~~N=N——N=N—N=N"^^)=tj H03S^ AcHN^ AcHN H3C Hd^~ ho3s^^ (1)-16 so3h so3h ^so3h Cl—N=N—C~^—N=N——N=N""C~>y—N=N— H03S^ AcHH AcHU h3c ho7" yS h3c#J^ so3h (1)-17 S03H S03H /T-S03H /^CWCN Cl—N=N——N=N——Ν=Ν-^λ~^—N= N-^ %:n Ho}^ AC^T h/^ H>V, (1)-18 so3h so3h ^^so3h js-7^ ^^^3S_/cn Cl—N=N—~N=N— —N=N—^~^—N=N—H03S》"~^ AgHN Corpse AcHN H2Q HC» Y^YS0^H h3〇-M 28 201237111 [Table 4] Compound number structure formula (1)-19 sd3h So3h so3h ^°^^3Cy_/CN H03S^ AcHN^ AcHhi H3C; ΗΟ^~ V^) ^so3h (D-20 S03H μ〇ζΗ S03H J/-<0"H3V<cn ChH^-N=N- N=N—N=N-^>-N=N-^^ HOjS~^ AcHN Wide AcHt/~ Bu 13. Guang HO y\ y ho3s (1)-21 S03H , S03H r-S02H JS-^ _/°"^Cv_J:N Cl_/~~y~N=N-~-N=N——N=N~^""^-N=N-^^=|s H03sT AcHN AcHN h3c HO HOAS (1)-22 so3h so3h ^^so3h s-^ o-^3ccn Ci-N=N——*N=N_'-N=N——N=N— HOzS AcHN AcHH H3C^ ΗΟ~ YK ^^so3h (1)-23 so3h so3h so3h 』 ^^^3CwCN CH^yN=N一—N=N——N=N——N=N—4^~Vs:n HOaS^ AcHN^ AcHN Plant H3C Factory HO yS, S〇3H (1)-24 5〇3H yS03H S03H Cl s-7^ __/3-/Γ^3〇\_/:ΝCl^yN=N——N= N—^~~^~N=N—^~^—N=N—H03s~^ AcHN Plant AcHN H3C^ HO^ ho3s 29 201237111 [Table 5]

化合物编號結構式 (1)-25. SOgH S03H /S03H H03S-Q^N=N—^~N=N-N=N- AcHN^ AcHN^ H3C： ΗΟ^ '^yCH3 SO3H ⑴.26 S03H ^03Η ^β03Η ^ Ac^r H3«r Η>ψ〇Η, ho3s (1)-27 SO3H j503H _^03H s-^ ^^Η3〇)_ν〇Ν HQ3S—^~~^-N=N——N=N~C3—N=N-^)=N AcHN~^ AcHN H3C HO NV=^yCH3 ⑴-28 SO3H S〇3H S〇3H S-^ s-y- P^OyP^ H03S—^~~^-Ν=Ν—C~^—N=N——Ν=Ν~^λΥ^ν AcHN AcHN HZC H0^l}l H3C so3h (1)-29 ^so3h jso3h so3h S^~ 0-^3C CN HOaS—-^~^-N=N—<C~^—N=N——N=N—-N= N-4~|V：n AcHN~ AcHN~ H3C^ HO H3C^^S〇3H ⑴-30 S03H ySOzH S03H ?u H3〇PN H〇3S_HC3"N=N""N=NC~~!/~N=N-N=N-^V：N AcHN AcHN H3Ci HO 30 201237111 [表6] 化合物編號結構式 ⑴-31 so3h so3h so3h Js^ 〇^H3〇VPN AcHN~ AcHN厂 H〆 HQ V^S03H och3 (1)-32 so3h so3h vso3h s-/ HaCs_J：N ho3sh〇>-n=n--^^n=n--^^—N=N-^T^N=N-\_\：N AcHN AcHN~ H3C厂 HC> H〇3s-JyJ H3CO (1)-33 so3h so3h jso3h t」~ f」~ ^n-^TigC^CN H03S—/~^N=N—\/)~N=N—ζ~^~N=N—™N=N™^/=r^ AcHN AcHN H3C HO N'|^n^S03h h3co (1)-34 jS03H S03H JS03H rJ^ _Ρ^"Η3〇)_^Ν H03S—^^-N=N—N=N——N=N"j"~^~N=N— AcHN^ AcHN^ H3C： HO~ Υ\ S^〇ch3 so3h (1)-35 so3h so3h 严 3h H03S—^~~^-Ν=Ν—~N=N——N=N—Ν=Ν-γ~ν：Ν AcHN广 AcHN广 H3(厂 HO ho3sa^OCh3 (1)-36 so3h ^o3h so3h HO3S——ζ^-'Ν=Ν-"C^J—Ν=ΙΨΗ^^—N=N—^JV：N ACHN AcHN H3C HO NV^S03H ^och3 31 201237111 [表7] 化合物編號結構武 (1)-37 so3h so3h so3h H03S-^3~n=n~C^y~N=N™X_^~N=N~\T/)~^N~^C AcHN AcHN H3C HO ⑴-38 so3h so3h so3h H〇3S—N=N—C~^—N=N——N=N——N=N-\_)5:N AcHN AcHN H3C HO NV^-CH3 ho3s (1)-39 so3h so3h so3h H3\/CN H 03S—N=N 一—N=N—一N=N——N=N-^\：n AcHN AcHN H3C HO^~%^VCH3 (1)-40 so3h ^o3h ^o3h ^*^3(v7:n H03s—^~^~N=N—C~^~N=N一—N=N——N=N-^j)=rN AcHNl AcHN H3C HO h3cV so3h ⑴.41 ^o3h so3h ^o3h s-/ s-^ P~^l〇\_PH H03S-^^-N=N-N=N—N=N-<^-N=N-^^^ AcHN广 AcHN广 H3C~ HO V^j H3C〜^S03H (1)-42 so3h jso3h so3h CN Cl—N=N——N=N——*N=N——N=N—^)=n H03s^ AcHN AcHN H3C HO NWVS03H h3c-V^ 32 201237111 [表8] 化合物編號結構式 (1)-43 503H S03H S03H HQ3S—^~^--N=N-N=N-"—N=N- C 厂 AcHN广 AcHN厂 H3C~ HO VS) (1)-44 so3h so3h ^o3h MS^ ^^cwCN H〇3$—N=N——N=N—N=N-N Cl· AcHN广 AcHN广 H3C： HC> yS HOzS^J h3co (1)-45 so3h so3h so3h rJ>^z〇)-fH H03s—^^-N=N——N=N——N=N-sT^—N=N-^"^n ΟΓ AcHN AcHN^ H0 N^VS〇3H H3CO (1)-46 so3h so3h _^o3h P~^ -Ρ~^Ηί(\-Ρ^ H03S-<^>-N=M-^>-N=N—N=N-^^—N=N-^)=^ cr AcHN7-^ AcHN厂 H3C HO~ V^OCHj so3h (1)-47 S03H ^SOsH so3h S-^ P-^C^N ho3s-^^~n=n—n=n~<^-~n=n-^>-n=n-^>^ cr AcHN^ AcHN^ HjC HO ^jj HOsS^^ch, (1)-48 so3h 7S03H so3h ,s-/ P^jC： CN H03S-^""V*n=n——N=N—C~^—N=N— ac^)^ Ac^~^ ^och3 33 201237111 [表9] 化合物編號結構式 ⑴-49 so3h so3h so3h h〇3s-hwkn=n'_^C^n=n—*0^n=n^C/ AcHN^ AcHN^ AcHN^ HO V^yCH3 ^'SOaH ⑴·50 so3h so3h so3h _》」~ 》」~ __P~~/H3C^CN H〇3$—N=N-"~N=Nζίί~N=N—Ν=Ν—^Λ=：ν AcHN AcHN AcHN HO Nj^|<CH3 ho3s (1)-51 so3h so3h so3h s-^ P^Z\^PU HQ3S—N=N——N=N—^^—*N=N——N=N-^^/^N AcHN AcHN AcHN HO (1)-52 SO3H S03H SOaH H03s—^^-N=N—N=N-^~^—N=M-N=N-AcHN^ AcHN^ AcHN~ HO ΗζΟ^γ1 S03H (1)-53 so3h /ο3η so3h ^^S-1 ~ 0-'^HgC CN HO3S—N=N——N=N—N=N-N=N- AcHN^ AcHN^ AcHN~ HO V^S h3c^^S03H (1)-54 S03H j03H jS03H p-' H03s—^~^~N=N——N=N—N=N''^/—^n_y/^=:N AcHN AcHN AcHN HO Ν^γ503Η 34 201237111 [表 ίο] 化合物編號結構式 ⑴.55 so3h so3h so3h o-^h3c conh2 Cl—N=N——N=N——N=N—^/=rM WO-β AcHN~ AcHN^ H3C^ HO^ S^so3h och3 (1)-56 so3h so3h so3h S-^ <D'j/H3qC〇NH2 Cl—N=N一—N=N——N=N--^"~^—N=N— H03S^ AcHN~ AcHN~ h3c ho γ\ h3co (1)-57 ^503H S03H SO3H S-/ /s*^ P^H3C conh2 CI~^"~^~N=N——f^N—N=N-™^^%tN H03s^ AcHN^ AcHN^ H3C ho ^γδ〇3Η h3co ⑴-58 S03H βΟζΗ S03H P-^3C： conh2 H03s广 AcHN广 AcHN厂 H3C~ HO OCH3 S03H (1)-59 S〇3H S〇3H S03H β-^ 0^H3CCONH2 Cl"^~~^~N=N—C~]^—N=N——N=N—N=N-^^=：N H03S^ AcHN~ AcHN~ H3C HO y^j| ho3sa^Ch3 (D-60 ^o3h so3h S03H S-/ J5-^ p-^zQ^QO^ CI~~C3-N=N—C3—"N=N~~~C~^y—N=N— H03£i AcHN^ AcHN卜 H:，C” HO’ ^Sch3 35 201237111 [表 11] 化合物編號結構式 ⑴-61 so3h so3h so3h /-f /-<0~^3<y-<CN Cl—N=N——N=N——N=N——N=N— ho3s^ achn achn achn H〇/~ 7ifCH3 ^^so3h (1)-62 so3h so3h so3h r-t^ J>^3〇PN Cl—N=N——N=N—N=N~"^~~^— H03S AcHN AcHN AcHN HO^^y0^ HOgS (D-63 ^o3h so3h so3h N=N——N=N-N=N— H03S AcHN^ AcHN^ f\cHU HO V^V0^ ho3s*^^ (1)-64 so3h so3h so3h s-^ —P^ ^^zCyfH N=N—N=N-^^—N=N-^^r^ H03S^ AcHN~ AcHN^ AcHN HO h3c*^V^ so3h (D-65 so3h so3h so3h N=N_^^—N=N-^>—N=N-·^^ HOaS" AcHN广" AcHN广 AcHN HO V^S h3C^^>s〇3h (1)-66 so3h so3h so3h J)~/r^3C\HpN α·Η^-Ν=Ν—N=N—N=N_^^-N=N~<^^ H03S尸 AcHN广 AcHN广 AcHN HO V^SOaH h3cA^ 36 201237111 [表 12] 化合物编號結構式 (1)-67 so3h so3h so3h CN S-/ ^°^r^3CWCN —^~"^~N=N—"N=N—N=N— HOgS^ AcHN~ AcHN~ H3C~ HO t^so3h 〇ch3 (1)-68 so3h so3h so3h CN Cl—N=N一—N=N——N=N~^~^—N=N—^~~/=^N HO^ Ac H3r VS HOaS-^y^ H3CO (1)-69 SOjH S03H S03H CN S-/ ^Ρ~^ζ〇\-ΡΗ Cl—/-N^N—V*-N=N—N=N-^ /=r|s| Ho/^ A^T A^f H3c/ (1)-70 S03H S03H J503H CN S-^ ,^^Η3〇ν_7〇ΝΙ Ch™/^y-N=N——N=N——Ν=Ν~Ηλ^^—N=N— HOaS^ AcHN~ AcHN~ H3C~ HO^ S^och3 so3h (1)-71 so3h so3h so3h ^CN 产」f ^》」~丨 ^〇-->/ΓΗ3〇^CN CI—^~y—N=N-*—N=N—-N=N——N=N— H03S^ AcHN~ AcHN~ h3c~ ho yS ho3s^\ch3 (1)-72 so3h ,so3h so3h _PN fr^ P^OpN CH-^7~Ν=Ν一C~^—N=N——N=N—N=N—^""VrN HOaS^ AcHN AcHN H3C HO NWv^s〇3H ^OCH3 37 201237111 [表 13]Compound No. (1)-25. SOgH S03H /S03H H03S-Q^N=N—^~N=NN=N-AcHN^ AcHN^ H3C: ΗΟ^ '^yCH3 SO3H (1).26 S03H ^03Η ^ Η03Η ^ Ac^r H3«r Η>ψ〇Η, ho3s (1)-27 SO3H j503H _^03H s-^ ^^Η3〇)_ν〇Ν HQ3S—^~~^-N=N——N= N~C3—N=N-^)=N AcHN~^ AcHN H3C HO NV=^yCH3 (1)-28 SO3H S〇3H S〇3H S-^ sy- P^OyP^ H03S—^~~^-Ν= Ν—C~^—N=N——Ν=Ν~^λΥ^ν AcHN AcHN HZC H0^l}l H3C so3h (1)-29 ^so3h jso3h so3h S^~ 0-^3C CN HOaS—-^ ~^-N=N-<C~^-N=N——N=N--N= N-4~|V:n AcHN~ AcHN~ H3C^ HO H3C^^S〇3H (1)-30 S03H ySOzH S03H ?u H3〇PN H〇3S_HC3"N=N""N=NC~~!/~N=NN=N-^V:N AcHN AcHN H3Ci HO 30 201237111 [Table 6] Compound number structure formula (1) -31 so3h so3h so3h Js^ 〇^H3〇VPN AcHN~ AcHN Factory H〆HQ V^S03H och3 (1)-32 so3h so3h vso3h s-/ HaCs_J:N ho3sh〇>-n=n--^^n =n--^^—N=N-^T^N=N-\_\:N AcHN AcHN~ H3C Factory HC> H〇3s-JyJ H3CO (1)-33 so3h so3h jso3h t”~ f”~ ^n-^TigC^CN H03S—/~^N=N—\/)~N=N—ζ~^~N=N—TMN=NTM^/=r^ AcHN A cHN H3C HO N'|^n^S03h h3co (1)-34 jS03H S03H JS03H rJ^ _Ρ^"Η3〇)_^Ν H03S—^^-N=N—N=N——N=N"j&quot ;~^~N=N— AcHN^ AcHN^ H3C: HO~ Υ\ S^〇ch3 so3h (1)-35 so3h so3h 严3h H03S—^~~^-Ν=Ν—~N=N——N =N—Ν=Ν-γ~ν:Ν AcHN wide AcHN wide H3 (factory HO ho3sa^OCh3 (1)-36 so3h ^o3h so3h HO3S——ζ^-'Ν=Ν-"C^J—Ν =ΙΨΗ^^—N=N—^JV:N ACHN AcHN H3C HO NV^S03H ^och3 31 201237111 [Table 7] Compound number structure Wu (1)-37 so3h so3h so3h H03S-^3~n=n~C ^y~N=NTMX_^~N=N~\T/)~^N~^C AcHN AcHN H3C HO (1)-38 so3h so3h so3h H〇3S—N=N—C~^—N=N— —N=N——N=N-\_)5:N AcHN AcHN H3C HO NV^-CH3 ho3s (1)-39 so3h so3h so3h H3\/CN H 03S—N=N —N=N—One N=N——N=N-^\:n AcHN AcHN H3C HO^~%^VCH3 (1)-40 so3h ^o3h ^o3h ^*^3(v7:n H03s—^~^~N=N— C~^~N=N一—N=N——N=N-^j)=rN AcHNl AcHN H3C HO h3cV so3h (1).41 ^o3h so3h ^o3h s-/ s-^ P~^l〇\_PH H03S-^^-N=NN=N-N=N-<^-N=N-^^^ AcHN Wide AcHN Wide H3C~ HO V^j H3C~^S03H (1)-42 so3h jso3h so3h CN Cl —N=N— —N=N——*N=N——N=N—^)=n H03s^ AcHN AcHN H3C HO NWVS03H h3c-V^ 32 201237111 [Table 8] Compound number structure formula (1)-43 503H S03H S03H HQ3S —^~^--N=NN=N-"—N=N- C Factory AcHN Guang AcHN Factory H3C~ HO VS) (1)-44 so3h so3h ^o3h MS^ ^^cwCN H〇3$—N =N——N=N—N=NN Cl· AcHN Wide AcHN Wide H3C: HC> yS HOzS^J h3co (1)-45 so3h so3h so3h rJ>^z〇)-fH H03s—^^-N=N ——N=N——N=N-sT^—N=N-^"^n ΟΓ AcHN AcHN^ H0 N^VS〇3H H3CO (1)-46 so3h so3h _^o3h P~^ -Ρ~ ^Ηί(\-Ρ^ H03S-<^>-N=M-^>-N=N-N=N-^^-N=N-^)=^ cr AcHN7-^ AcHN Factory H3C HO ~ V^OCHj so3h (1)-47 S03H ^SOsH so3h S-^ P-^C^N ho3s-^^~n=n-n=n~<^-~n=n-^>-n =n-^>^ cr AcHN^ AcHN^ HjC HO ^jj HOsS^^ch, (1)-48 so3h 7S03H so3h ,s-/ P^jC: CN H03S-^""V*n=n ——N=N—C~^—N=N— ac^)^ Ac^~^ ^och3 33 201237111 [Table 9] Compound number structure formula (1)-49 so3h so3h so3h h〇3s-hwkn=n'_^ C^n=n—*0^n=n^C/ AcHN^ AcHN^ AcHN^ HO V^yCH3 ^'SOaH (1)·50 so3h so3h so3h _》”~ 》”~ __P~~/H3C^CN H〇 3$ —N=N-"~N=Nζίί~N=N—Ν=Ν—^Λ=:ν AcHN AcHN AcHN HO Nj^|<CH3 ho3s (1)-51 so3h so3h so3h s-^ P^Z \^PU HQ3S—N=N——N=N—^^—*N=N——N=N-^^/^N AcHN AcHN AcHN HO (1)-52 SO3H S03H SOaH H03s—^^-N =N—N=N-^~^—N=MN=N-AcHN^ AcHN^ AcHN~ HO ΗζΟ^γ1 S03H (1)-53 so3h /ο3η so3h ^^S-1 ~ 0-'^HgC CN HO3S —N=N—N=N—N=NN=N- AcHN^ AcHN^ AcHN~ HO V^S h3c^^S03H (1)-54 S03H j03H jS03H p-' H03s—^~^~N=N ——N=N—N=N′′^/—^n_y/^=:N AcHN AcHN AcHN HO Ν^γ503Η 34 201237111 [Table ί ] Compound No. Structure (1).55 so3h so3h so3h o-^h3c conh2 Cl —N=N——N=N——N=N—^/=rM WO-β AcHN~ AcHN^ H3C^ HO^ S^so3h och3 (1)-56 so3h so3h so3h S-^ <D'j /H3qC〇NH2 Cl—N=N—N=N——N=N--^"~^—N=N— H03S^ AcHN~ AcHN~ h3c ho γ\ h3co (1)-57 ^503H S03H SO3H S-/ /s*^ P^H3C conh2 CI~^"~^~N=N——f^N—N=N-TM^^%tN H03s^ AcHN^ AcHN^ H3C ho ^γδ〇3Η H3co (1)-58 S03H βΟζΗ S03H P-^3C: conh2 H03s wide AcHN wide AcHN plant H3C~ HO OCH3 S03H (1)-59 S 3H S〇3H S03H β-^ 0^H3CCONH2 Cl"^~~^~N=N—C~]^—N=N——N=N—N=N-^^=:N H03S^ AcHN~ AcHN ~ H3C HO y^j| ho3sa^Ch3 (D-60 ^o3h so3h S03H S-/ J5-^ p-^zQ^QO^ CI~~C3-N=N-C3—"N=N~~~ C~^y—N=N—H03£i AcHN^ AcHNb H:,C” HO' ^Sch3 35 201237111 [Table 11] Compound number structure (1)-61 so3h so3h so3h /-f /-<0~ ^3<y-<CN Cl-N=N——N=N——N=N——N=N— ho3s^ achn achn achn H〇/~ 7ifCH3 ^^so3h (1)-62 so3h so3h so3h Rt^ J>^3〇PN Cl—N=N——N=N—N=N~"^~~^— H03S AcHN AcHN AcHN HO^^y0^ HOgS (D-63 ^o3h so3h so3h N= N——N=NN=N— H03S AcHN^ AcHN^ f\cHU HO V^V0^ ho3s*^^ (1)-64 so3h so3h so3h s-^ —P^ ^^zCyfH N=N—N=N -^^—N=N-^^r^ H03S^ AcHN~ AcHN^ AcHN HO h3c*^V^ so3h (D-65 so3h so3h so3h N=N_^^—N=N-^>—N=N -·^^ HOAS" AcHN widely" AcHN wide AcHN HO V^S h3C^^>s〇3h (1)-66 so3h so3h so3h J)~/r^3C\HpN α·Η^-Ν=Ν —N=N—N=N_^^-N=N~<^^ H03S Corpse AcHN Wide AcHN Wide AcHN HO V^SOaH h3cA^ 36 201237111 [Table 12] Compound Structural formula (1)-67 so3h so3h so3h CN S-/ ^°^r^3CWCN —^~"^~N=N—"N=N—N=N— HOgS^ AcHN~ AcHN~ H3C~ HO T^so3h 〇ch3 (1)-68 so3h so3h so3h CN Cl—N=N一—N=N——N=N~^~^—N=N—^~~/=^N HO^ Ac H3r VS HOaS-^y^ H3CO (1)-69 SOjH S03H S03H CN S-/ ^Ρ~^ζ〇\-ΡΗ Cl—/-N^N—V*-N=N—N=N-^ /=r |s| Ho/^ A^TA^f H3c/ (1)-70 S03H S03H J503H CN S-^ ,^^Η3〇ν_7〇ΝΙ ChTM/^yN=N——N=N——Ν=Ν ~Ηλ^^—N=N— HOaS^ AcHN~ AcHN~ H3C~ HO^ S^och3 so3h (1)-71 so3h so3h so3h ^CN "f ^""~丨^〇-->/ΓΗ3〇 ^CN CI—^~y—N=N-*—N=N—N=N—N=N—H03S^ AcHN~ AcHN~ h3c~ ho yS ho3s^\ch3 (1)-72 so3h ,so3h So3h _PN fr^ P^OpN CH-^7~Ν=Ν一C~^—N=N——N=N—N=N—^""VrN HOaS^ AcHN AcHN H3C HO NWv^s〇3H ^OCH3 37 201237111 [Table 13]

化合物編號結構式 (1)-73 so3h so3h so3h p^q>pn ci-hQ-n=n-hP>-n=n-^-n=n^P^n=n-〇=n H03S^ AcHN~ AcHN^ AcHN~ HO^ YifCHi (1)-74 JS03H so3H 户 03H ON Cl~N=NN=N——N=N——N=N-\^)==N H03s^ AcHN卜 AcHU AcHU HO y^V°H3 ho3s (1)-75 S03H S03H ySOzH pu S-^-^ yS"^"~^ ^°^H3V-<，：N ct—^~^-N=N——N=N——N=N-^^—N=N-4^=N ho3s^ achn^ achn achn ho Ί^γ0Η3 HOjsAJ (1)-76 so3h so3h SO3H CN S-^ /S"^ ^"^3CWCN Cl~~^~/-N=N一一N=N—-N=N~"C~>/N=N-^—V：N HO^ Ao^ Ac^T ACH^ SO3H (1)-77 S03H S03H 5〇3H ^CN ^$」~^ ^S—^Ρ-^ΗίΟ^CN Cl~N=N——N=N—ζ/)-"N=N—-N=N— HOjS^ AcHN~ AcHN~^ AcHN HO Y\ H3C'^A'S〇3H (1)-78 S03H j£503H S03H CN ^^^3CWCN CI—/^-N=N~N=N—C3~Ν^"^^~Ν=Ν—N H03S^ AcHN^ AcHN*"^ H</~ J^Y^〇3H 38 201237111 [表 14]Compound number structure formula (1)-73 so3h so3h so3h p^q>pn ci-hQ-n=n-hP>-n=n-^-n=n^P^n=n-〇=n H03S^ AcHN ~ AcHN^ AcHN~ HO^ YifCHi (1)-74 JS03H so3H Household 03H ON Cl~N=NN=N——N=N——N=N-\^)==N H03s^ AcHN BuAcHU AcHU HO y ^V°H3 ho3s (1)-75 S03H S03H ySOzH pu S-^-^ yS"^"~^ ^°^H3V-<,:N ct-^~^-N=N——N=N ——N=N-^^—N=N-4^=N ho3s^ achn^ achn achn ho Ί^γ0Η3 HOjsAJ (1)-76 so3h so3h SO3H CN S-^ /S"^ ^"^3CWCN Cl ~~^~/-N=N一一N=N—N=N~"C~>/N=N-^—V:N HO^ Ao^ Ac^T ACH^ SO3H (1)- 77 S03H S03H 5〇3H ^CN ^$"~^ ^S—^Ρ-^ΗίΟ^CN Cl~N=N——N=N—ζ/)-"N=N—-N=N— HOjS ^ AcHN~ AcHN~^ AcHN HO Y\ H3C'^A'S〇3H (1)-78 S03H j£503H S03H CN ^^^3CWCN CI—/^-N=N~N=N—C3~Ν^" ^^~Ν=Ν—N H03S^ AcHN^ AcHN*"^ H</~ J^Y^〇3H 38 201237111 [Table 14]

化合物編號結構式 (1)-79 so3h so3h so3h CN S-/ CN CHH^)-N=N—N=N—f^— WO-β AcHti AcHN~ AcHN^ HO S^so3h och3 (1)-80 so3h so3h so3h CN S-/ Cl—N=N—^~~^~N=N——N=N——N=N-^^VrN H03S^ AcHN^ AcHN^ AcHN~ HO HOaS-^Y^1 h3co (1)-81 so3h so3h so3h CN /°^/^cyJ:N ci_^kn=n_O~n=n^0>—ν=ν_Ό_ν=ν_Οϊ^ WQ-d~J AcHN AcHN AcHN HO 'j^^S03H HjCO (1)-82 so3h so3h so3h Cl—^ N=N—《》—N=N—^》—N=N—^ ^—N=N—^ )=rN HOzS AcHN AcHN AcHN HO so3h CH3 (1)-83 so3h so3h so3h CN fN CH^~^-N=N——N=N-*—Ν==Ν-^ζ^ H03S^ AcHN~ AcHN AcHN HO ho3s"^^〇CH3 (1)-84 jS03H S03H S03H CN S-^ ^~^3<V-/N Cl—^"y-N=N—\))—N=N——N=N— Ac^ir AOHN^ h>^03H 39 201237111 [表 15] 化合物編號結構式 (1)-85 S〇3H S〇3H JSO3H /CN CI~^^-N=N-N=N-^^-N=N-<^)—N=N-<^=：义 H〇3 厂 AcHN厂 AcH 厂 H3(厂 HC* ^S〇3H (1)-86 SO3H SO3H S〇3H CN ^^^3CWCN Cl~~^"~^~N=N——N=N——N=N——N=N^ ho3s^ achn^ achn^ h3c ho^~Nnj^^ch3 ho3s (1)-87 so3h so3h S03H Pu N C t—N=N一C》~N=N—^》—N=N—^》—N=N^^^==N H03S^ AcHN AcHN H3C HO Wv-CH3 ho3s^^ (1)-88 S03H jS03H SO3H CN s-^ ^'^3<V-/：N Ch-N=N一—N=N——N=N—「^-N=N-H03S广 AcHN广 AcHN广 H3C： HO厂 h3(tV 503H (1)-89 S03H S03H μ〇^Η CN S-/ _/S-^ ^"^3CWCN Cl—N=NN=N~~~N=N— H03S^ AcHN^ AcHN~^ h3c~ HO jT^jj h3c^^S03H (1)-90 S03H S03H S03H JN S-/ ^'^3<VJ：N CH-/t~N=N—ζ~~}—N=N~~ζ~^—N=N-^~"^~N=N—^~V=n Η〇>^ AcJ^ H^r 40 201237111 [表 16] 化合物編號結搆式 (D-91 so3h ^o3h so3h O-^C CN Cl~~N=N—N=N——N=N—(x^^·—N=N— HOOC AcHN^ AcHN^ AcHN HO VSj S^so3h 〇ch3 (1)-92 S03H 户 03H jS03H p-^3(ypu Cl—^~~^-N=N——N=N—N=N-^~^—N=N— HOOC^ AcHN~ AcHN~ AcHN HO V^| HOzS^\J H3C0 (1)-93 S03H ^03H iS03H Cl—N=N—N=N——N=N-^a~~^—ΙΦ=Ν-^^)=：ν HOOC AcHN AcHN AcHN HO h3co (1)-94 so3h so3h so3h Cl—N=N——N=N——N=N~^T^y—N=N—^~V=n HOOC~^ AcHn"^ AcHN^ AcHN~ η0^ΓΪ1 S^〇ch3 so3h ⑴-95 so3h ,S03H so3h s-^ CN C!~/*~^—N=N—~N=N——N=N——N=N— HOOC~"^ AcHN^ AcHN^ AcHN~ HO Y\ ho3sa^OCh3 ⑴-96 so3h so3h so3h Cl—N=N——N=N——·N=N--^~~^-N=N~"^~^m H0〇c/"^ AcHN AcHN^ AcHN H〇" V^s〇3H och3 41 201237111 v ()所示之化合物之重氮化，係以其的方法來實施，^, 例如：在無機酸介質中，在例如_5〜3 〇。〇、較佳為0〜15*^·^、之溫度，使用亞硝酸鹽實施，亞硝酸鹽係例如亞硝酸鈿玺=, 納等亞硝酸鹼金屬鹽。上述式（7、祕- , 不之化合物之重氮化物與上述式（8)所示之化合物之叙八 . 0 ’亦在其本身為習知的條件下實施。以在下述條件下進杆私& + 較為有利：在水或水性有機介質中，在例如-5〜3 0 〇C、動杜达為〇〜25 C之溫度，且在酸性〜中性之 pH值、例如Compound number structural formula (1)-79 so3h so3h so3h CN S-/ CN CHH^)-N=N-N=N-f^- WO-β AcHti AcHN~ AcHN^ HO S^so3h och3 (1)-80 So3h so3h so3h CN S-/ Cl—N=N—^~~^~N=N——N=N——N=N-^^VrN H03S^ AcHN^ AcHN^ AcHN~ HO HOaS-^Y^1 H3co (1)-81 so3h so3h so3h CN /°^/^cyJ:N ci_^kn=n_O~n=n^0>—ν=ν_Ό_ν=ν_Οϊ^ WQ-d~J AcHN AcHN AcHN HO 'j^^ S03H HjCO (1)-82 so3h so3h so3h Cl—^ N=N—“—N=N—^”—N=N—^ ^—N=N—^ )=rN HOzS AcHN AcHN AcHN HO so3h CH3 ( 1)-83 so3h so3h so3h CN fN CH^~^-N=N——N=N-*—Ν==Ν-^ζ^ H03S^ AcHN~ AcHN AcHN HO ho3s"^^〇CH3 (1)- 84 jS03H S03H S03H CN S-^ ^~^3<V-/N Cl—^"yN=N—\))—N=N——N=N— Ac^ir AOHN^ h>^03H 39 201237111 [Table 15] Compound No. Structural Formula (1)-85 S〇3H S〇3H JSO3H /CN CI~^^-N=NN=N-^^-N=N-<^)-N=N-&lt ;^=: Yi H〇3 Plant AcHN Plant AcH Plant H3 (Factory HC* ^S〇3H (1)-86 SO3H SO3H S〇3H CN ^^^3CWCN Cl~~^"~^~N=N- —N=N——N=N——N=N^ ho3s^ achn^ achn^ h3c ho^~Nnj^^ch3 ho3s (1)-87 so3h so 3h S03H Pu NC t—N=N_C”~N=N—^”—N=N—^”—N=N^^^==N H03S^ AcHN AcHN H3C HO Wv-CH3 ho3s^^ (1 )-88 S03H jS03H SO3H CN s-^ ^'^3<V-/:N Ch-N=N-N=N——N=N—“^-N=N-H03S Wide AcHN Wide AcHN Wide H3C : HO厂h3(tV 503H (1)-89 S03H S03H μ〇^Η CN S-/ _/S-^ ^"^3CWCN Cl—N=NN=N~~~N=N— H03S^ AcHN^ AcHN~^ h3c~ HO jT^jj h3c^^S03H (1)-90 S03H S03H S03H JN S-/ ^'^3<VJ:N CH-/t~N=N-ζ~~}—N=N ~~ζ~^—N=N-^~"^~N=N—^~V=n Η〇>^ AcJ^ H^r 40 201237111 [Table 16] Compound number structure (D-91 so3h ^o3h so3h O-^C CN Cl~~N=N-N=N——N=N—(x^^·—N=N— HOOC AcHN^ AcHN^ AcHN HO VSj S^so3h 〇ch3 (1) -92 S03H Household 03H jS03H p-^3(ypu Cl—^~~^-N=N——N=N—N=N-^~^—N=N— HOOC^ AcHN~ AcHN~ AcHN HO V^ HOZS^\J H3C0 (1)-93 S03H ^03H iS03H Cl—N=N—N=N——N=N-^a~~^—ΙΦ=Ν-^^)=:ν HOOC AcHN AcHN AcHN HO h3co (1)-94 so3h so3h so3h Cl—N=N——N=N——N=N~^T^y—N=N—^~V=n HOOC~^ AcHn"^ AcHN^ AcHN~ Η0^ΓΪ1 S^〇ch3 so3h (1)-95 so3h ,S0 3H so3h s-^ CN C!~/*~^—N=N—~N=N——N=N——N=N— HOOC~"^ AcHN^ AcHN^ AcHN~ HO Y\ ho3sa^OCh3 (1)-96 so3h so3h so3h Cl-N=N——N=N——·N=N--^~~^-N=N~"^~^m H0〇c/"^ AcHN AcHN^ AcHN H〇" V^s〇3H och3 41 201237111 The diazotization of the compound shown by v() is carried out by a method thereof, for example, in a mineral acid medium, for example, _5 to 3 Torr. The temperature of 〇, preferably 0 to 15*^·^, is carried out using nitrite, and the nitrite is, for example, cerium nitrite =, an alkali metal nitrite such as sodium. The above formula (7, the secret, the diazotide of the compound and the compound of the above formula (8) are also carried out under the conditions of the prior art, and are carried out under the following conditions. Private & + is more advantageous: in water or aqueous organic medium, for example, -5 to 30 〇C, moving Dudda is 〇~25 C, and at acidic to neutral pH, for example

ptl1〜6。由於重氮化反應液為酸性，並且反應系統内會因A .^ 進仃耦合反應而更加酸性化，故經由添加鹼 ::液之pH值調整成較佳pH條件。鹼能夠使用例磁醯：飞鋰、虱氧化鈉等鹼金屬之氫氧化物；碳酸鋰、碳酸鈉、碳酸鈿#π, ^ 々“一屬之碳酸鹽；乙酸鈉等乙酸鹽；氨或有機胺專。 =工（）所不之化合物及上述式（8)所示之化合物，係使用大約化學計量的量。的方= :(:)所示之化合物之重氮化，係以其本身為習知 =方法來貫施，例如：在無機酸介質中，在例如·5〜4〇。卜較佳為5〜3〇°c之、、田电之恤度，使用亞硝酸鹽實施，亞硝酸睡俜例如亞頌酸鋼等亞硝酸驗金屬鹽。以酸瓜係之仆人：所不之化合物之重氮化物與上述式(10)所示之化合物之耦人，v J1 下述裕杜ΠΓ * Q '、在其本身為習知的條件下實施。以在如-5〜贼、較“ 或水性有機介質中’在例較佳為H)〜3〇t之溫度，且在酸性〜中性之 42 201237111 pH 值、例如 DJq·，，， γ ρ 2〜7。由於重氮化反應液為酸性，並且反應系統内會因推± λ 哭订耦合反應而更加酸性化，故經由添加驗來將反應液之ηΜ # # & 〇 & PH值調整成較佳ρΗ條件。鹼能夠使用與上述相同者。上述式（9)所示之化合物及上述式（10)所示之化合物，係使用大約化學計量的量。上述式（11)所示之化合物之重氮化，係以其本身為習夫的方法來實施’例如：在無機酸介質中，在例如-5〜 50 C較佳為5〜40°C之溫度，使用亞硝酸鹽實施，亞硝酸鹽係例如亞硝酸鈉等亞硝酸鹼金屬鹽。上述式（11)所示之化合物之重氮化物與上述式（12)所示之化0物之耦合，亦在其本身為習知的條件下實施。以在下述條件下進行較為有利：在水或水性有機介質中在例如-5〜5(TC、較佳為1〇〜4〇t之溫度，且在酸性〜中性之pH值、例如pH2〜7。由於重氮化反應液為酸性，並且反應系統内會因進行耦合反應而更加酸性化，故經由添加鹼來將反應液之pH值調整成較佳pH條件。鹼能夠使用與上述相同者。上述式（11)所示之化合物及上述式（12)所示之化合物，係使用大約化學計量的量。上述式（13)所示之化合物之重氮化，係以其本身為習知的方法來實施，例如：在無機酸介質中，在例如_5〜 50 C、較佳為1 〇〜40 C之溫度，使用亞硝酸鹽實施，亞硝酸鹽係例如亞硝酸鈉等亞硝酸鹼金屬鹽。 43 201237111 之化合物之重氮化物與上述式（14)& 不之化合物之耦合， /、上述式（14)所兀在其本身為習知的條# 在下述條件下進行較為 ’、 ·《施。以 ,,,,.。〜有利.在水或水性有機介質中，在例如-5〜50°C、較佳Α 。，貝1Τ在柹少為0〜40C之溫度.，且在弱酸性〜鹼 “PH值。較佳是在弱酸性〜】〇實施，PH值之調整俜經…：：阳值、例如PH5 與上述相同者。整係、、“添加鹼來霄施。驗能約使用物上述式（13)所示之化合Μ上述式（14)所*之化合物，係使用大約化學計量的量。 '、、本發明之墨水組成物所含之色素(II)，為-種以上的上述式（2)所7F之色素。換言之，色素（II)可為上述式（2)所示之單-色f ’亦可為上述式⑺所示之複數種色素之混合物’以單一色素為佳。上述式（2)中，A及B分別獨立地表示：笨基；萘基；或具有1個偶氮鍵之基，該等基可經從由羥基、磺基、羧基及（C1〜C4)院基羰基胺基所構成之群組中選出之至少 —種基所取代。其中，較佳是A及B分別獨立地為··具有從由磺基及羧基所構成之群組中選出之至少一種取代基且具有1個偶氮鍵之基。上述式（2)中’取代基A、B之具體例係如下述所示，但並不一定受此等例子所限定。再者，下述具體例中之氺記號’係意指在該位置與上述式（2)之偶氮鍵鍵結。 201237111 苯基：、<} ho3sPtl1~6. Since the diazotization reaction liquid is acidic, and the reaction system is more acidic due to the A. coupling reaction, the pH value of the alkali addition solution is adjusted to a preferable pH condition. The alkali can be used as a hydroxide of an alkali metal such as fly ash or sodium bismuth oxide; lithium carbonate, sodium carbonate, cesium carbonate #π, ^ 々 "a carbonate of one genus; an acetate such as sodium acetate; ammonia or organic The compound of the formula (8) and the compound of the above formula (8) are used in an amount approximately stoichiometric. The diazotization of the compound represented by the formula: :(:) is based on itself. For the conventional method, for example, in a mineral acid medium, for example, 5 to 4 Torr, preferably 5 to 3 〇 °c, and Tiantian's degree, using nitrite, Nitrite sleeps such as linoleic acid steel and other nitrite metal salts. The servant of the melons: the compound of the diazotide and the compound of the above formula (10), v J1 Rhododendron *Q', is carried out under its own conditions, in the form of a temperature such as -5 to thief, "or in an aqueous organic medium, preferably H" to 3 〇t, and is acidic. ~ Neutral 42 201237111 pH, for example DJq·, , , γ ρ 2~7. Since the diazotization reaction solution is acidic, and the reaction system is more acidic due to the push-to-λ cryo-coupling reaction, the ηΜ## &〇& PH value of the reaction solution is adjusted to be better by adding the test. ρΗ condition. The base can be used in the same manner as described above. The compound represented by the above formula (9) and the compound represented by the above formula (10) are used in an amount approximately stoichiometric. The diazotization of the compound represented by the above formula (11) is carried out by itself as a method of 'fuss', for example, in a mineral acid medium, for example, 5 to 50 C, preferably 5 to 40 ° C. The temperature is carried out using nitrite, and the nitrite is an alkali metal nitrite such as sodium nitrite. The coupling of the diazotide of the compound represented by the above formula (11) with the chemical represented by the above formula (12) is also carried out under the conditions known per se. It is advantageous to carry out under the following conditions: in water or an aqueous organic medium, for example, at a temperature of -5 to 5 (TC, preferably 1 Torr to 4 Torr, and at an acidic to neutral pH, for example, pH 2 〜 7. Since the diazotization reaction liquid is acidic, and the reaction system is more acidic due to the coupling reaction, the pH of the reaction liquid is adjusted to a preferable pH condition by adding a base. The alkali can be used in the same manner as described above. The compound represented by the above formula (11) and the compound represented by the above formula (12) are used in an amount approximately stoichiometric. The diazotization of the compound represented by the above formula (13) is known per se. The method is carried out, for example, in a mineral acid medium, for example, at a temperature of _5 to 50 C, preferably 1 Torr to 40 C, using nitrite, and a nitrite such as nitrite such as sodium nitrite The salt of the compound of the compound of the formula (14) & · · "..,,,,,.. ~. Benefit. In water or water In the organic medium, for example, -5 to 50 ° C, preferably Α., Τ 1 Τ is less than 0 to 40 ° C., and is weakly acidic ~ alkali "pH value. It is preferably weakly weak ~" 〇 In the implementation, the pH value is adjusted by::: a positive value, for example, PH5 is the same as the above. The whole system, "addition of alkali to apply. The test can be used as shown in the above formula (13). 14) The compound of the present invention is a stoichiometric amount. The dye (II) contained in the ink composition of the present invention is a dye of 7F of the above formula (2). In other words, the pigment (II) The single-color f' represented by the above formula (2) may be a mixture of a plurality of pigments represented by the above formula (7), preferably a single dye. In the above formula (2), A and B respectively Independently represented: stupid; naphthyl; or a group having one azo bond, which may be from a group consisting of a hydroxyl group, a sulfo group, a carboxyl group, and a (C1 to C4)-based carbonylamino group. The at least one selected group is substituted. Among them, preferably, A and B are each independently selected from at least one selected from the group consisting of a sulfo group and a carboxyl group. The substituent has a group of one azo bond. The specific examples of the substituents A and B in the above formula (2) are as follows, but are not necessarily limited by these examples. The 氺 mark ' in the specific example means the azo bond at the position with the above formula (2). 201237111 Phenyl: , <} ho3s

so3h ho3s' "~^ ^—S〇3H * \So3h ho3s' "~^ ^—S〇3H * \

so3hSo3h

HOOCHOOC

P〇〇H NHCOCH3 HO、 * —nhcoch3 *P〇〇H NHCOCH3 HO, * —nhcoch3 *

so3h 萘基： •t»So3h naphthyl: •t»

so3Hso3H

S〇3H H03SS〇3H H03S

OHOH

OHS.H ·执。，~QCT3H so3h 〇hOHS.H · Executive. ,~QCT3H so3h 〇h

具有1個偶氮鍵之基： /=\ 一 HCA group with one azo bond: /=\ one HC

ho3S、 ho3s、 N=N—^^>-S03H · N=Nho3S, ho3s, N=N—^^>-S03H · N=N

ho3sHo3s

SO3HSO3H

N=N^^ H03SN=N^^ H03S

S〇3HS〇3H

HOaSHOaS

V-/ S〇3HV-/ S〇3H

S〇3H 上述式（2)中之取代基A、B可分別獨立，代基之組合為佳’亦即色素⑼以對稱結構為佳。目同的取作為色素（Π)較佳的組合之具體例 18所示。下述表17、 45 201237111 [表 17]S〇3H The substituents A and B in the above formula (2) may be independently used, and the combination of the substituents is preferable, that is, the dye (9) is preferably a symmetric structure. The same applies to the specific example 18 which is a preferable combination of the pigment (Π). Tables 17, 45 201237111 [Table 17]

化合物編號結構式 ⑵·1 OH OH 人 V 人八^So3h Η Η ⑵.2 OH OH _/C00H <Q^N=N—o p^-^u-0 人卩人^^S03H Η Η (2)-3 HOOC 〇Η 〇H COOH ^n=n~]&l X X55rN=N_^ Η H ⑵-4 OH OH <〇H-N=N—rpv^j 0 —N=N-^J>-NHC0CH3 Η H ⑵-5 OH OH y^V u ^~N=N~^C\ X χΎ^Ν=Ν_〇^" Η038Λ^^ΝΑΝ^^Λ503Η Η Η ⑵-6 h〇3s~C^^n=n_^Cq xyVn=n~^^~s〇3H Η H 46 201237111 [表 18]Compound number structure formula (2)·1 OH OH person V person eight^So3h Η Η (2).2 OH OH _/C00H <Q^N=N-op^-^u-0 person 卩人^^S03H Η Η (2 )-3 HOOC 〇Η 〇H COOH ^n=n~]&l X X55rN=N_^ Η H (2)-4 OH OH <〇HN=N-rpv^j 0 —N=N-^J>- NHC0CH3 Η H (2)-5 OH OH y^V u ^~N=N~^C\ X χΎ^Ν=Ν_〇^" Η038Λ^^ΝΑΝ^^Λ503Η Η Η (2)-6 h〇3s~C^ ^n=n_^Cq xyVn=n~^^~s〇3H Η H 46 201237111 [Table 18]

化合物编號結搆式 ⑵-7 HOjS^n=n_^_n=n_^^ n=n^hn=n_Qks〇3h H〇3S 人，^人^As〇3H w Η Η ⑵·8 ㈣〇^n〇-so3h 人^As〇jH Η Η ⑵-9 Η。心才=:?5a^c5c;賞分 s°3H h〇3S H H H〇jh ⑵，10 JSO3H 〇h H。吟：今:成:喊 S〇sH Η H S03H 其中 ’ C.I. Direct Orange 26、C.I. Direct Orange 29、 C.I. Direct Red 4、C.I. Direct Red 23、C.I. Direct Red 80，係能夠以市售染料之形式取得，並且在製作成黑色墨水使用時，顯色性、牢固性、溶劑溶解性優異，因而較佳。並且’以C.I. Direct Red 80特別有用。上述之標示有C.I.編號之染料，能夠以購入市售染料並藉由習知手法來精製成適於喷墨之純度之方式使用，亦能夠容易地按照解說染料化學（由色染社所發行）十所記载之合成方法，從市售原料合成。本發明之墨水組成物，可包含一種以上的上述式〇)所示之色素作為色素⑽。換言之，色素（111)可為上述式⑺ 47 201237111 所不之單—色素’亦可為上述式⑺所示之複數種色素之混合物，以單一色素為佳。上述式（3)中，Rat，無取代（C1〜C4)烷基可舉例如：直鏈或支鏈之無取代（C1〜C4)烷基，以直鏈為佳^具體例可舉例如.甲基、乙基、正丙基' 正丁基等直鏈無取代 C4)烧基’異丙基、異丁基、二級丁基、三級丁基等支鍵無取代（C1〜C4)烷基等。其中，以甲基、乙基、正丙基為佳，以曱基特佳。Compound number structure (2)-7 HOjS^n=n_^_n=n_^^ n=n^hn=n_Qks〇3h H〇3S person, ^人^As〇3H w Η Η (2)·8 (4)〇^n〇 -so3h person ^As〇jH Η Η (2)-9 Η. Heart ==?5a^c5c; reward points s°3H h〇3S H H H〇jh (2), 10 JSO3H 〇h H.吟:今:成:叫S〇sH Η H S03H where 'CI Direct Orange 26, CI Direct Orange 29, CI Direct Red 4, CI Direct Red 23, CI Direct Red 80, can be obtained in the form of commercially available dyes. Further, when it is used as a black ink, it is excellent in color developability, firmness, and solvent solubility, and thus is preferable. And 'C.I. Direct Red 80 is especially useful. The above-mentioned dyes with the CI number can be used in a manner suitable for the purity of inkjet by purchasing commercially available dyes, and can also be easily used according to the explanation of dye chemistry (issued by the color dyeing agency). The synthesis method described in ten is synthesized from commercially available raw materials. The ink composition of the present invention may contain one or more dyes represented by the above formula ()) as the dye (10). In other words, the pigment (111) may be a single pigment of the above formula (7) 47 201237111, or a mixture of a plurality of pigments represented by the above formula (7), and a single pigment is preferred. In the above formula (3), the cyclic, unsubstituted (C1-C4) alkyl group may, for example, be a linear or branched unsubstituted (C1-C4) alkyl group, preferably a straight chain. Specific examples include, for example. Linear, unsubstituted C4) alkyl, ethyl, n-propyl 'n-butyl, etc., unsubstituted, such as isopropyl, isobutyl, secondary butyl, tert-butyl, etc. (C1~C4) Alkyl and the like. Among them, a methyl group, an ethyl group, and a n-propyl group are preferred, and a thiol group is preferred.

Ra中’經羥基或（C1〜C4)烷氧基所取代之（C1〜C4)烷基可舉例如：直鏈或支鏈之經羥基或（C1〜C4)烷氧基所取代之（C1〜C4)烷基，以直鏈為佳。具體例可舉例如：2羥基乙基等羥基取代（C1〜C4)烷基；甲氧基乙基、乙氧基乙基、正丙氧基乙基、異丙氧基乙基、正丁氧基乙基、二級丁氧基乙基、三級丁氧基乙基等（C1〜C4)烷氧基取代（C1 〜C4)烷基等。The (C1 to C4) alkyl group substituted by a hydroxyl group or a (C1 to C4) alkoxy group in Ra may be, for example, a linear or branched hydroxy group or a (C1 to C4) alkoxy group (C1). ~C4) alkyl, preferably linear. Specific examples thereof include a hydroxy-substituted (C1 to C4) alkyl group such as a 2-hydroxyethyl group; a methoxyethyl group, an ethoxyethyl group, a n-propoxyethyl group, an isopropoxyethyl group, and a n-butoxy group; (C1 to C4) alkoxy group-substituted (C1 to C4) alkyl group, etc., such as a ethyl group, a secondary butoxy group, a tertiary butoxy group or the like.

Ra中’無取代（C1〜C4)烷氧基可舉例如：直鏈或支鏈之無取代（C1〜C4)烧氧基’以直鏈為佳。具體例可舉例如：曱氧基、乙氧基、正丙氧基、正丁氧基等直鏈無取代（Ci 〜C4)烷氧基；異丙氧基、異丁氧基、二級丁氧基、三級丁氧基等支鏈無取代（C1〜C4)烷氧基等。其中，以曱氧基、乙氧基、正丙氧基為佳，以甲氧基特佳。The unsubstituted (C1-C4) alkoxy group in Ra may, for example, be a straight-chain or branched unsubstituted (C1-C4) alkoxy group. Specific examples thereof include a linear unsubstituted (Ci-C4) alkoxy group such as a nonyloxy group, an ethoxy group, a n-propoxy group or a n-butoxy group; an isopropoxy group, an isobutoxy group, and a secondary butyl group; A branched unsubstituted (C1 to C4) alkoxy group such as an oxy group or a tertiary butoxy group. Among them, a decyloxy group, an ethoxy group, and a n-propoxy group are preferred, and a methoxy group is particularly preferred.

Ra中，經羥基或（C1〜C4)烷氧基所取代之（C1〜C4)烷氧基可舉例如：直鏈或支鏈之經羥基或（C1〜C4)烷氧基所取代之（C1〜C4)烷氧基，以直鏈為佳。具體例可舉例如： 48 201237111 2-羥基乙氧基、2-羥基丙氧基、3_羥基丙氧基等羥基取代（ci 〜C4)烧氧基，甲氧基乙氧基、乙氧基乙氧基、正丙氧基乙氧基、異丙氧基乙氧基、正丁氧基乙氧基、甲氧基丙氧基、乙氧基丙氧基、正丙氧基丙氧基、異丙氧基丁氧基、正丙氧基丁氧基等直鏈或支鏈（較佳為直鏈）之（C1〜C4)烧氧基取代（C1〜C4)烷氧基；2-羥基乙氧基乙氧基等複合取代有羥基及烷氧基之（C1〜C4)烷氧基等。In the Ra, the (C1 to C4) alkoxy group substituted by a hydroxy group or a (C1 to C4) alkoxy group may be, for example, a linear or branched hydroxy group or a (C1 to C4) alkoxy group ( C1 to C4) alkoxy group, preferably a linear chain. Specific examples include, for example, 48 201237111 2-hydroxyethoxy group, 2-hydroxypropoxy group, 3-hydroxypropyloxy group and the like hydroxy-substituted (ci-C4) alkoxy group, methoxyethoxy group, ethoxy group Ethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, a linear or branched (preferably linear) (C1 to C4) alkoxy group substituted with a (C1 to C4) alkoxy group such as isopropoxybutoxy or n-propoxybutoxy; 2-hydroxyl The (C1 to C4) alkoxy group having a hydroxyl group and an alkoxy group is substituted by an ethoxyethoxy group or the like.

Ra中’無取代（C1〜C4)烷基胺基可舉例如：甲基胺基、乙基胺基、正丙基胺基、異丙基胺基、正丁基胺基、異丁基胺基等單（無取代之直鏈或支鏈烷基）胺基；N，N_二甲基胺基、N，N -二乙基胺基、N，N-二正丙基胺基、n，N-二異丙基胺基等二（無取代之直鏈或支鏈烧基）胺基等。The 'unsubstituted (C1 to C4) alkylamine group in Ra may, for example, be a methylamino group, an ethylamino group, a n-propylamino group, an isopropylamino group, an n-butylamino group or an isobutylamine. A single (unsubstituted linear or branched alkyl) amine group; N,N-dimethylamino, N,N-diethylamino, N,N-di-n-propylamino, n a N (disubstituted straight or branched alkyl) amine group such as N-diisopropylamino group.

Ra中，經羥基或（C1〜C4)烷氧基所取代之（C1〜C4)院基胺基可舉例如：羥基乙基胺基、2-羥基丙基胺基、3 -經基丙基胺基等單（羥基取代烧基）胺基；雙（羥基乙基）胺基等雙（羥基取代烷基）胺基；曱氧基乙基胺基、乙氧基乙基胺基等單（烷氧基取代烷基）胺基；雙（曱氧基乙基）胺基、雙（2_ 乙氧基乙基）胺基等雙（烷氧基取代烷基）胺基等。In the Ra, the (C1 to C4)-based amine group substituted by a hydroxyl group or a (C1-C4) alkoxy group may, for example, be a hydroxyethylamino group, a 2-hydroxypropylamino group or a 3-propylpropyl group. a mono(hydroxy-substituted alkyl)amino group such as an amine group; a bis(hydroxy-substituted alkyl)amino group such as a bis(hydroxyethyl)amino group; a methoxyethylamino group, an ethoxyethylamino group or the like ( An alkoxy-substituted alkyl)amino group; a bis(alkoxy-substituted alkyl)amino group such as a bis(methoxyethyl)amino group or a bis(2-ethoxyethyl)amino group; and the like.

Ra中，羧基（C1〜C5)烷基胺基可舉例如：直鏈或支鏈之羧基（C 1〜C5)烷基胺基’以直鏈為佳。具體例可舉例如：羧基甲基胺基、羧基乙基胺基、羧基丙基胺基、羧基正丁基胺基、羧基正戊基胺基等。In the Ra, the carboxyl group (C1 to C5) alkylamine group may, for example, be a linear or branched carboxyl group (C 1 to C5) alkylamine group. Specific examples thereof include a carboxymethylamino group, a carboxyethylamino group, a carboxypropylamino group, a carboxy-n-butylamino group, and a carboxy-n-pentylamino group.

Ra中，雙（羧基（C1〜C5)烷基）胺基可舉例如：直鏈或支鏈之雙（羧基（C1〜C5)烷基）胺基，以直鏈為佳。具體例 49 201237111 可舉例如：雙（羧基甲基）胺基、雙（羧基乙基）胺基、雙（羧基丙基）胺基等^In Ra, the bis(carboxy(C1~C5)alkyl)amino group may, for example, be a linear or branched bis(carboxy(C1-C5)alkyl)amino group, preferably a straight chain. Specific Examples 49 201237111 For example, a bis(carboxymethyl)amino group, a bis(carboxyethyl)amino group, a bis(carboxypropyl)amino group, etc.

Ra中，無取代（C1〜C4)烷醯基胺基可舉例如··直鏈或支鏈之無取代（C 1〜C4)烷醯基胺基’以直鏈為佳。具體例可舉例如：乙醯基胺基、正丙醯基胺基等直鏈之無取代（C1 〜C4)烷醯基胺基；異丙醯基胺基等支鏈之無取代（C1〜C4) 烷醯基胺基等。In Ra, the unsubstituted (C1 to C4) alkanoylamino group may, for example, be a straight chain or a branched unsubstituted (C 1 to C 4 ) alkanoylamino group. Specific examples include a linear unsubstituted (C1 to C4) alkanoylamino group such as an acetamino group or a n-propylamino group; and an unsubstituted group such as an isopropylidene group (C1~) C4) an alkanoylamino group or the like.

Ra中’經羥基或（C1〜C4)烷氧基所取代之（C1〜C4)烷酿基胺基可舉例如：直鏈或支鏈之經羥基或（C 1〜C4)烧氧基所取代之（C 1〜C4)炫醯基胺基’以直鏈為佳。具體例可舉例如：羥基乙醯基胺基、2-羥基正丙醯基胺基、3_羥基正丙醯基胺基、2-羥基正丁醯基胺基、3-羥基正丁醯基胺基等羥基取代（C1〜C4)烷醯基胺基；2-甲氧基正丙醯基胺基、3-甲氧基正丙醯基胺基、2-甲氧基正丁醯基胺基、3- 曱氧基正丁醯基胺基等烷氧基取代（C1〜C4)烷醯基胺基等。The (C1 to C4) alkylaryl group substituted by a hydroxyl group or a (C1 to C4) alkoxy group in Ra may, for example, be a linear or branched hydroxyl group or a (C 1 to C 4 ) alkoxy group. The substituted (C 1 -C4) fluorenylamino group is preferably a straight chain. Specific examples thereof include a hydroxyl group such as a hydroxyethylamino group, a 2-hydroxy-n-propylamino group, a 3-hydroxy-n-propylamino group, a 2-hydroxy-n-decylamino group, or a 3-hydroxy-n-decylamino group. Substituting (C1~C4) alkanoylamino group; 2-methoxy-n-propylamino group, 3-methoxy-n-propylamino group, 2-methoxy-n-decylamino group, 3-oxime An alkoxy group such as a n-butyl group is substituted with a (C1 to C4) alkanoylamino group or the like.

Ra中，苯環經從由羧基、磺基及胺基所構成之群組中選出之至少一種基所取代之苯基胺基之例子可舉例如：2-叛基苯基胺基、3-羧基苯基胺基、4-羧基苯基胺基、3,5-二羧基苯基胺基等羧基取代苯基胺基；2-磺基苯基胺基、 3·磺基苯基胺基、4-磺基苯基胺基等磺基取代苯基胺基； 2·胺基苯基胺基、j，5-二胺基苯基胺基等胺基取代苯基胺基；二胺基磺基苯基胺基等分別取代有磺基及胺基之苯基胺基等。 50 201237111 上述中，Ra以無取代（C1〜C4)烷基為佳，其中以甲基特佳。上述式（3)中’ X中’經羧基或磺基所取代之脂肪族胺基可舉例如.直鏈或支鏈（較佳為直鏈）之續基（C1〜C5)院基胺基；直鏈或支鏈（較佳為直鏈）之羧基〜C5)烷基胺基，直鏈或支鏈（較佳為直鏈）之二（續基（C1〜C5)炫基）胺基’直鏈或支鏈（較佳為直鏈）之二（羧基（C1〜C5)烷基）胺基等直鏈或支鏈（較佳為直鏈）之經羧基或磺基所取代之單 (C1〜C5)烷基胺基或二（（C1〜C5)烷基）胺基等。碳數之範圍通常為C1〜C5 ’以C1〜C4為佳，以C1〜C3較佳，以 C1〜C2更佳。具體例可舉例如：磺基曱基胺基、磺基乙基胺基、磺基丙基胺基、磺基丁基胺基、磺基戊基胺基等磺基（cl〜c5) 烷基胺基；羧基曱基胺基、羧基乙基胺基、羧基丙基胺基、羧基丁基胺基、羧基戊基胺基等羧基（C1〜C5)烷基胺基；二（磺基f基）胺基、二（磺基乙基）胺基、二（磺基丙基）胺基等二（磺基（C1〜C5)烷基）胺基；二（羧基曱基）胺基等二（缓. 基（C1〜C5)烷基）胺基等。上述中’ X以續基（C1〜C5)烷基胺基、二（羧基（C1〜 C5)烷基）胺基為佳’以磺基（Ci〜C5)烷基胺基較佳，其中以磺基乙基胺基特佳。上述式（3)所示之色素（m)中’以上述式（4)所示之色素為佳。式（4)中，X係包含為佳者等在内，均表示與上述式 (3)中之X相同的意義。 51 201237111 上素最佳述式（3)所示之色素（Ιπ)中以下述式（15)所示之色 ho3sIn Ra, examples of the phenylamine group in which the benzene ring is substituted with at least one selected from the group consisting of a carboxyl group, a sulfo group and an amine group may, for example, be a 2-repoylphenylamino group, 3- a carboxy-substituted phenylamino group such as a carboxyphenylamino group, a 4-carboxyphenylamino group or a 3,5-dicarboxyphenylamino group; a 2-sulfophenylamino group; a 3-sulfophenylamino group; a sulfo-substituted phenylamino group such as a 4-sulfophenylamino group; an amine-substituted phenylamine group such as an aminophenylamino group or a j-5-diaminophenylamino group; and a diaminosulfonyl group; The phenylamino group or the like is substituted with a phenylamino group having a sulfo group and an amine group, and the like, respectively. 50 201237111 In the above, Ra is preferably an unsubstituted (C1 to C4) alkyl group, and particularly preferably a methyl group. The aliphatic amine group substituted by a carboxyl group or a sulfo group in 'X' in the above formula (3) may, for example, be a linear or branched (preferably linear) contiguous group (C1 to C5). a linear or branched (preferably linear) carboxy to C5) alkylamino group, a linear or branched (preferably linear) bis (cont. (C1 to C5) leu) amine group a single linear or branched (preferably linear) bis (carboxy (C1 to C5) alkyl) amine group such as a straight or branched (preferably linear) substituted by a carboxyl group or a sulfo group (C1 to C5) an alkylamino group or a di((C1~C5)alkyl)amino group or the like. The range of the carbon number is usually C1 to C5', preferably C1 to C4, more preferably C1 to C3, and even more preferably C1 to C2. Specific examples thereof include a sulfo (cl~c5) alkyl group such as a sulfoalkylamino group, a sulfoethylamino group, a sulfopropylamino group, a sulfobutylamino group or a sulfopentylamino group. a carboxyl group (C1 to C5) alkylamine group such as an amino group; a carboxymethylamino group, a carboxyethylamino group, a carboxypropylamino group, a carboxybutylamino group or a carboxypentylamino group; a bis(sulfo(C1~C5)alkyl)amino group such as an amine group, a bis(sulfoethyl)amino group or a bis(sulfopropyl)amino group; a di(carboxymethyl)amino group; A group of (C1~C5)alkyl)amino groups and the like. In the above, 'X is preferably a C1-C5 alkylamino group or a di(carboxy(C1~C5)alkyl)amine group, preferably a sulfo(Ci~C5)alkylamine group, wherein Sulfoethylamine is particularly preferred. In the dye (m) represented by the above formula (3), the dye represented by the above formula (4) is preferred. In the formula (4), the X system is preferably the same as the X in the above formula (3), and the like. 51 201237111 The best color in the pigment (Ιπ) shown in the above formula (3) is the color shown by the following formula (15) ho3s

πυ3δ, 上述式（3)所示之色素（⑴），能夠按昭專利記載之方法獲得。夜”、、專利文獻3中所Πυ3δ, the dye ((1)) represented by the above formula (3) can be obtained by the method described in the patent publication. "Night", Patent Document 3

i^^~S03h (15) 本發明之墨水組成物，可包含氣篡之氽治k J匕3 1刀子中具有1〜2個偶 ^性黃色染料作為色素(IV) (ΙΠ)中所含之色素除外。（）此處，所謂水溶性黃色染料，係指分子中具有磺基、幾基而具有對水之溶解性之染料，具體而言可舉例如：對水之溶解性顯示5Qg/kg以上之溶解性之色素。具有上述溶解性之色素’以顯示8〇g/kg以上之溶解性之色素為佳，以 100 g/kg以上較佳。作為色素（IV)之具體例，能夠使用習知的黃色色素（例如：C.I. Direct Yeilow 34、C I Direct Yell〇w 58、C I Directi^^~S03h (15) The ink composition of the present invention may contain a gas 篡 k k J 匕 3 1 knives having 1 to 2 azo yellow dyes as contained in the pigment (IV) (ΙΠ) Except for the pigment. (a) The water-soluble yellow dye is a dye having a sulfo group or a few groups in the molecule and having solubility in water. Specifically, for example, the solubility in water is 5Qg/kg or more. Sexual pigment. The dye having the above solubility is preferably a pigment exhibiting solubility of 8 〇 g/kg or more, preferably 100 g/kg or more. As a specific example of the dye (IV), a conventional yellow pigment can be used (for example, C.I. Direct Yeilow 34, C I Direct Yell〇w 58, C I Direct

Yellow 86 > C.I. Direct Yellow 120 > C.I. Direct Yellow 132 ^ C.L Direct Yellow 142等）’上述所列舉之色素中，以c.i. Direct Yellow 86、C.I. Direct Yellow 132、C.I. Direct Yellow 142 為佳，以 C.I. Direct Yellow 132 較佳。色素（IV)之具體例較佳可舉例如下述式（16)所示之色素或其鹽（以下’基於與上述同樣的理由，包含「色素或其鹽」兩者在内，均簡略記載為「色素」）。 52 201237111 與標示有上述C.I.編號之各染料相比，使用下述式（16) 所示之色素作為色素（IV)之墨水，能夠獲得一種印刷物因而較佳’該印刷物係耐光性、耐臭氧性更優異，特別是耐濕性更優異 n(HQ3S)Yellow 86 > CI Direct Yellow 120 > CI Direct Yellow 132 ^ CL Direct Yellow 142, etc. 'In the above-mentioned pigments, ci Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 142 are preferred, CI Direct Yellow 132 is preferred. Specific examples of the dye (IV) include a dye represented by the following formula (16) or a salt thereof (hereinafter, 'including a pigment or a salt thereof for the same reason as described above), and are simply described as "pigment"). 52 201237111 A dye represented by the following formula (16) is used as the ink of the dye (IV) as compared with each of the dyes having the above-mentioned CI number, and it is possible to obtain a printed matter, which is preferable in that the printed matter is light-resistant and ozone-resistant. More excellent, especially moisture resistance is better n (HQ3S)

0(CH2)qS03H N=NΝ=Ν1^Ι -(S03H)m0(CH2)qS03H N=NΝ=Ν1^Ι -(S03H)m

NH R H03S. /(CH2)y (16) 上述式（16)中，R表示氫原子、無取代（ci〜c4)烷基、無取代（C1〜C4)院氧基、或續基，η表示表示丄〜3之整數’ q表示2〜4之整數’ y表示1〜3之整數，當虛線所不之環不存在瞎，& > ’取代有-(S〇3H)m之環表示苯環，當虛線所示之環在為_ & 、取代有_(S〇3H)m之環表示萘環。上述式（16)所示之色辛 T為单一色素，亦可為上述式 (16)所不之複數種色辛 "、 I之/昆合物’以單一色素為佳。上述式（16)中，r中，|取包含為佳者等在内，均愈上、=C1〜C4)烧基可舉例如：〜叫燒基相同者。〜切心以之無取代⑹ 等二，:^：=，氧基可舉例如:包含為佳者、上返式（3)中之Ra^ 相同者。之…、取代（C1〜C4)烷氧基上述中，R以無取甲氧基特佳。 C4)烷氧基為佳，其中，以為佳 53 201237111 未限定取代位置之「_ (S〇3H)n」，其在苯環上的取代位置係無特別限制，當該苯環上之氮原子的取代位置為ι 位且η為2時’以2位及4位為佳。同樣地，n為}時，以4位為佳。上逑式（16)中未限定取代位置之「一（S〇3H)rn」，其在所取代之環上的取代位置係無特別限冑。該環不具有虛線所示之環時、亦即為苯環時m，並且當該苯環上之氮原子的取代位置為i位時，「-（S〇3H)m」w取代在3位較佳。同樣地，該環具有虛線所示之環時、亦即為萘環時，功為2，並且當該蔡環狀之氮原子的取代位置為2 取代在5位及7位、6位及8位或4位及8位較佳。上述式（16)中，Μ 2〜4之整數，以3為佳。此外，y為1〜3之整數，以2為佳。 5、〇(CH2)3S03H Kl kt 上述式⑽所示之色素以下述式（17)所示 HO3S、 ^(CHg^SOaH 色素為佳 N^N Jh 6 ,(CH2)2NH R H03S. /(CH2)y (16) In the above formula (16), R represents a hydrogen atom, an unsubstituted (ci~c4) alkyl group, an unsubstituted (C1 to C4) alkoxy group, or a contiguous group, η An integer representing 丄~3 'q means an integer of 2 to 4' y represents an integer of 1 to 3, and when the dotted line does not exist, &> 'replaces a ring of -(S〇3H)m The benzene ring is represented by a ring represented by a broken line in the form of _ & and a ring substituted with _(S〇3H)m represents a naphthalene ring. The coloring unit T represented by the above formula (16) is a single coloring matter, and may be a single coloring matter of a plurality of coloring compounds ", I/coin compound of the above formula (16). In the above formula (16), in the case where r is contained, the ratio of ? is more preferably, and the ratio of C1 to C4) is, for example, the same. ~Cut the heart without substitution (6), etc., :^:=, the oxy group can be, for example, the inclusion of the best one, and the upper return type (3) of Ra^ are the same. In place of (C1 to C4) alkoxy group, R is particularly preferred as the methoxy group. C4) alkoxy group is preferred, wherein, in the case of 53 53371111, the substitution position "_ (S〇3H)n" is not limited, and the substitution position on the benzene ring is not particularly limited, when the nitrogen atom on the benzene ring When the substitution position is ι and η is 2, '2 and 4 are preferred. Similarly, when n is }, 4 bits are preferred. In the above formula (16), "一(S〇3H)rn" of the substitution position is not limited, and the substitution position on the substituted ring is not particularly limited. When the ring does not have a ring indicated by a broken line, that is, when the benzene ring is m, and when the substitution position of the nitrogen atom on the benzene ring is i, "-(S〇3H)m"w is substituted at the 3 position. Preferably. Similarly, when the ring has a ring indicated by a broken line, that is, a naphthalene ring, the work is 2, and when the ring position of the nitrogen atom of the ring is 2, the substitution is at 5 and 7 positions, 6 positions, and 8 Bits or 4 and 8 are preferred. In the above formula (16), an integer of Μ 2 to 4 is preferably 3. Further, y is an integer of 1 to 3, preferably 2. 5. 〇(CH2)3S03H Kl kt The pigment represented by the above formula (10) is represented by the following formula (17): HO3S, ^(CHg^SOaH pigment is preferably N^N Jh 6 , (CH2) 2

k：3r*(S〇3H)L ho3s，一 (17) 上述式(17)中’R係包含為佳者等在内式（16)令之R相同的意義，L表示/表不與上述佳上述式（16)所示之色素中，以下述式^所1為佳。 )所不之色素最 54 201237111k: 3r*(S〇3H)L ho3s, one (17) In the above formula (17), the 'R system contains the same meaning as the R of the internal formula (16), and the L indicates/exhibits the above. Among the dyes represented by the above formula (16), the following formula is preferred. The color of the pigment is the most 54 201237111

0(CH2)3S03H 5~0~Ν=ΝΗ0~^γΝγ^Ό'^ SO3H (18) n^n \0(CH2)3S03H 5~0~Ν=ΝΗ0~^γΝγ^Ό'^ SO3H (18) n^n \

丫 ΟΜθ NH (6h2)2 ho3s’ 作為色素（IV)之水溶性黃色染料，其習知物能夠從市場容易地取得4外，上述式⑽所示之較佳結構之水溶性黃色染料’能夠按照專利文獻4中所記载之方法獲得。本發明之墨水組成物中所使用之色素、色素（II)、色素_及色素（IV)之鹽，為與無機陽離子或有機陽離子所生成之鹽。#中，與無機陽離子所生成之鹽可舉例如：驗金屬鹽、鹼土金屬鹽、及銨鹽’以鋰鹽 '鈉鹽，鹽、以及敍鹽為佳。另一方面’與有機陽離子所生成之鹽；舉例如與下述式(19)所示之四級銨所生成之鹽，但並不限定於此等。、此外，游離酸、其互變異構物、及該等之各種鹽混合物。可使用下述混合物 *'' 仕、σ例如：鈉鹽與鍵鹽之混合物；游離酸與鈉鹽之人· 爻戽σ物，鋰鹽、鈉鹽及銨睡之混合物等。有時溶解性等物性值會因鹽的種類而里，;: 夠經由因應需要而適當選擇鹽的種類、或當包含複b 等時經由使其比例改變等’來獲得具有 - 混合物。的之物性之 z1 ^—N+'Z2 23 (19) Z分別獨立地表在上述式（19)中，z1、z2、z3、不 55 201237111 氫原子；從由烷基、羥基烷基、及羥基烷氧基烷基所構成之群組令選出之基’且至少任一者表示氫原子以外之基。 • 上述式（19)中，Z、Z2、Z3、Z4之烧基之具體例可舉例如：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基等，羥基烷基之具體例可舉例如：羥基甲基、羥基乙基、3-羥基丙基、2-羥基丙基、4-羥基丁基、 3-羥基丁基、2-羥基丁基等羥基（C1〜C4)烷基。羥基烷氧基烷基之具體例可舉例如：羥基乙氧基甲基、2_羥基乙氧基乙基、3-羥基乙氧基丙基、2_羥基乙氧基丙基、4羥基乙氧基丁基、3-羥基乙氧基丁基、2_羥基乙氧基丁基等羥基 (C1〜C4)烷氧基（C1〜C4)烷基。此等中，以羥基乙氧基〜C4)烷基為佳。特佳者可舉例如：氫原子；甲基；羥基甲基、羥基乙基、3-羥基丙基、2-羥基丙基、4_羥基丁基、3· 羥基丁基、2_羥基丁基等羥基（C1〜C4)烷基；羥基乙氧基曱基、2-羥基乙氧基乙基、3_羥基乙氧基丙基、2·羥基乙氧基丙基、4-羥基乙氧基丁基、3_羥基乙氧基丁基、2_羥基乙氧基丁基等羥基乙氧基（C1〜C4)烷基等。上述式（19)所示之較佳化合物中，Z1、Z2、Z3及Z4之組合之具體例，係如下述表19所示。 56 201237111 [表 19] 化合物No. Z1 Ζ2 Z3 Z4 1-1 Η CH3 CH3 CH3 1-2 CH3 CH3 CH3 CH3 1-3 Η -C2H40H -C2H40H -C2H40H 1-4 CH3 -C2H40H -C2H40H -C2H40H 1-5 Η -CH2CH(0H)CH3 -CH2CH(0H)CH3 -CH2CH(0H)CH3 1-6 CH3 -CH2CH(OH)CH3 -CH2CH(0H) CH3 -CH2CH(0H)CH3 1-7 Η -C2H40H H -C2H40H 1-8 CH3 -C2H40H H -C2H40H 1-9 Η - CH2CH(OH)CH3 H -CH2CH(OH)CH3 1-10 CH3 -CH2CH(OH)CH3 H - CH2CH(OH)CH3 1-11 CH3 -C2H40H CH3 -C2H40H 1-12 CH3 -CH2CH(0H)CH3 CH3 -CH2CH(0H)CH3 以下說明本發明之墨水組成物。本發明之墨水組成物係包含色素（I)、色素（II)、或因應需要之色素（ΠΙ)及色素（IV)，能夠將由纖維素所構成之材料著色。此外，亦能夠對具有羧醯胺鍵之材料進行著色，而能夠廣泛用於皮革、織物、紙等材料。在進行色素（I)、色素（Π)、色素（III)及色素（IV)各自之合成反應時，最後步驟結束後之各自之反應液，能夠直接用於製造本發明之墨水組成物。然而，亦能夠藉由下述方式來單離出各色素後，將各色素混合，而調製墨水組成物：首先將包含各色素之反應液個別乾燥、例如噴霧乾燥；經由添加氯化鈉、氣化鉀、氯化鈣、硫酸鈉等無機鹽類來進行鹽析；經由添加鹽酸、硫酸、硝酸等礦酸來進行酸析；或是將上述之鹽析與酸析組合來進行酸鹽析等。本發明之墨水組成物，係包含色素（I)、色素（II)作為色 57 201237111 素此外’為了獲得更顯著的功效，因應需要而包含色素 (ΙΠ)及’或色素（IV)。色素⑴、色素（II)、色素（III)，分別可在滿足上述特定條件之範圍内為單獨的色素，亦可分別為複數種色素之混合物。此外，色素（1¥)為i分子中具有1 〜2個偶氮基之化合物且為水溶性黃色染料。因此，本發明之墨水組成物，係調配有至少2種以上的色素，並因應需要而調配有4種以上的色素。本發明之墨水組成物中所含之色素的總質量中，色素 ⑴之比例為50〜90質量％，以50〜8〇質量％為佳，色素 (Π)之比例為！〜10質量％，以1〜8質量％為佳。當調配色素（III)及/或色素(IV)時，色素（πι)之比例為5〜質量 ^以5〜15質董％為佳，色素（IV)之比例為4〜20質量 %，以4〜15質量％為佳。此外，相對於墨水組成物的總質量，色素（1)、色素（ιι)、以及需要時之色素（m)及色素（IV)的總含量通常為〇質里％，以1〜10質量％為佳，以2〜8質量％較佳。本發明之墨水組成物可復包含：水溶性有機溶劑例如〇〜30質量％、墨水調製劑例如〇〜2〇質量％，餘份為水。為了提高保存安定性之目的，本發明之墨水組成物之 ΡΗ以ΡΗ5〜η為佳，以ρΗ7〜ί〇較佳。此外，墨水組成物之表面張力以25〜7G mN/m為佳，以25〜6q⑽^較佳。並且，墨水組成物之黏度以3〇 mPa . s以下為佳，以 2〇mPa· s以下較佳。本發明之墨水組成物之pH;表面張力，能夠以如後所述之pH調整劍、界面活性劑來適當調整： 58 201237111 本發明之墨水組成物，係使色素⑴、色素（ιι)、色素（m) 及色素溶於水或水溶性有機溶劑（能夠與水混合的有機 :劑)中’並因應需要而加入墨水調製劑而成。當使用此墨水組成物作為嗔墨記錄用之墨水時’以使用本發明之墨水組成物所含之色素⑴、色素⑼、色素_及色素（IV)中之無機雜質的含量較少者為佳，該無機雜質為：金屬陽離子之氣化物（例如氯化鈉）、金屬陽離子之硫酸鹽（例如硫酸納）等。該無機雜質含量之基準，係相對於色素的總質量，大約為1質量％以下左右’下限為分析機器之偵測極限以亦即〇質量％即可。在製造無機雜質少的色素時，只、下述方法來進行除鹽處理即可，例如：藉由逆渗透膜之方法，在甲醇等（C1〜C4)醇類及水之混合溶劑中，將色素之乾燥物或濕濾餅攪拌後，過濾分離析出物並乾燥等之方法；使用離子交換樹脂將無機雜質進行交換吸附之方法等。在調製上述墨水組成物時，能夠使用之水溶性有機溶劑之具體例可舉例如：甲醇、乙醇、丙醇、異丙醇、丁醇办異丁醇、二級丁醇、三級丁醇等（C1〜C4)烷醇；N，化二曱曱醯胺、N，N-二曱基乙醯胺等羧醯胺；2_吡咯啶酮、… 土 2比咯咬酮、N-甲基η比嘻啶·2_酮等内醢胺類；丨，3_二甲基味唾咬-2’、I3-二曱基六氫癌。定-2-酮等環式脲類；丙鲷、甲基乙基酮、2-甲基-2-羥基戊-4-酮等酮類或酮醇類’四氫呋喃、二噚烷（dioxane)等環狀醚；乙二醇、12_ 丙一醇、1，3·丙二醇、1>2•丁二醇、1>4_丁二醇、16-己二 59 201237111 醇、二乙二醇、三乙二醇、四乙二醇、二丙二醇、聚乙二醇、聚丙二醇、硫二乙醇（thiGdigiy叫、二硫二乙醇等二有C2〜C6伸燒基單元之單、募聚或聚烧二醇或是硫乙：醇’甘油、己·1，2,6-三醇等多元醇（三元醇）；乙二醇單喊、乙二醇單乙基驗、^乙二醇單甲基醚、二乙二醇單乙基醚：二乙二醇單丁基醚(丁基卡必醇)、三乙二醇單甲基醚一乙一醇早乙基醚等多元醇之（C1〜C4)烷基醚；ρ丁㈣、二甲基亞颯（dimethylsulf〇xide)等。此等有機溶劑可單獨使用，亦可併用兩種以上。此等中，以異丙醇、Ν·甲基〜比略咬酮、甘油、丁美卡必醇等為佳。土在調製本發明之墨水組成物時，能夠適當使用之墨水調製劑可舉例如：防腐防霉劑、ΡΗ調整劑、鉗合試劑、防鏽劑、水溶性紫外線吸收劑、水溶性高分子化合物、色素合解J k氧化劑、界面活性劑等。以下說明此等墨水調製劑。防霉劑可舉例如：去氫乙酸鈉、苯曱酸鈉、巯基吡啶 •1·氧化物鋼鹽、對經基苯曱酸乙g旨、U苯并異嘆唾琳_3_ 酮 U，2-benzisothiaz〇lin_3 〇ne)及其鹽等。 /防腐劑可舉例如：有機硫系、有機氮硫系、有機函素系' _芳基砜系、碘炔丙基系、鹵烷硫基系、腈系、吡啶、毯基喹琳系、笨并嗟唑（benzothiazole)系、異噻唑啉 (isothlazoUne)系、二硫醇系、吡啶氧化物系硝基丙烷系、有機錫系、酚系、四級銨鹽系、三畊（triazine)系、噻D井 201237111 (thiazine)系、醯苯胺（anUide)系、金剛烷系、二硫代胺基甲酸醋系、溴茚酮（bromoindanone)系、溴乙酸苯甲g旨系無機鹽系等之化合物。有機齒素系化合物之具體例可舉例如五氣苯酚鈉，吼咬氧化物系化合物之具體例可舉例如2_巯基吡咬氧化物鈉鹽，異噻唑啉系化合物之具體例可舉例如：丨，I笨并異噻唑琳-3-酮、2-正辛基-4-異噻唑啉_3-酮、5-氣-2-曱夷4 異噻唑啉-3-酮、5-氯-2-曱基-4-異噻唑啉·3__氯化鎂、5_ 氣-2-甲基-4-異噻唑啉_3_酮氯化鈣、2-甲基_4-異噻唑啉_3_ 酮氣化鈣等。其他防腐防霉劑之具體例可舉例如：無水乙酸鈉、山梨酸鈉、苯曱酸鈉、或Arch Chemicals公司製商品名 Pr〇XelRTM GXL(S)或 ProxelRTM XL 2(S#。再者，在本說明書中’上標之「RTM」係意指註冊商標。 pH調整劑，係只要能夠在不對所調製之墨水造成不良影響之情形下將墨水之pH控制在例如5〜丨丨之範圍内，則能夠使用任意物質。其具體例可舉例如：二乙醇胺、三乙醇胺、N-甲基二乙醇胺等烷醇胺；氫氧化鋰、氫氧化鈉、氫氧化鉀等鹼金屬之氫氧化物；氫氧化銨（氨水）；碳酸鋰、碳酸鈉、碳酸氫鈉、碳酸鉀等鹼金屬之碳酸鹽；矽酸鈉、乙酸鉀等有機酸之鹼金屬鹽；磷酸氫二鈉等無機鹼等。鉗合試劑可舉例如：乙二胺四乙酸二鈉、氮基三乙酸鈉、羥基乙基乙二胺三乙酸鈉、二伸乙三胺五乙酸鈉、展嘧啶二乙酸鈉等。防鏽劑可舉例如：酸性亞硫酸鹽、硫代硫酸鈉、硫代 61 201237111 季戊四醇四硝酸酯、亞硝乙醇酸銨、亞硝酸二異丙基錢酸二環己基銨等。不洛性紫外綠吸收劑可舉例如經確化之下述化入物二苯甲酮系化合物、苯并三嗤系化合物、柳酸系化：物桂皮酸系化合物、三0井系化合物。聚乙烯醇、纖維素衍水溶性高分子化合物可舉例如生物、多胺、多亞胺等。己内醯胺、碳酸伸乙酯、尿色素溶解劑可舉例如素等。抗氧化劑能夠使用各種有機系及金屬錯合物系之防视色劑。有機系之防褪色劑.之例子可舉例如：氫職類、院氧基酚類、二烷氧基酚類、酚類、苯胺類、胺類、二氫節（indane) 類、色滿（chromane)類、烷氧基笨胺類、雜環類等。界面活性劑可舉例如··陰離子系、陽離子系、非離子系等之習知的界面活性劑。陰離子界面活性劑之例子可舉例如：烷磺酸鹽、烷基羧酸鹽、α-烯烴磺酸鹽、聚氧乙烯烷基醚乙酸鹽 (polyethylene alkyl ether acetate)、N-醯基胺基酸及其鹽、 N-醯基曱基牛磺酸鹽、烷基硫酸鹽聚氧烷基醚硫酸鹽、烷基硫酸鹽聚氧乙烯烧基醚填酸鹽、松香酸皂、蓖麻油硫酸酉曰鹽、月桂醇硫酸酯鹽、烧基紛型峨酸酯、院基型填酸酯、院基芳磺酸鹽、二乙基磺基琥珀酸鹽、二乙基己基磺基琥 ίό酸鹽、一辛基項基玻轴酸鹽等。陽離子界面活性劑之例子可舉例如：2-乙烯基吡啶衍 62 201237111 生物、聚（4-乙烯基吡啶）衍生物等。兩性界面活性劑之例子可舉例如：月桂基二甲基胺基乙酸甜菜驗、2-烧基基甲基I經基乙基,蝴鹽甜菜驗、椰子油脂賴絲丙U基胺基乙酸甜菜驗、聚辛基聚胺基乙基甘胺酸、或咪唑啉衍生物等。非離子界面活性劑之例子可舉例如：聚氧乙稀壬基苯基謎、聚氧乙烯辛基苯基⑽ ' 聚氧乙科4基苯基驗、聚氧乙烯油基醚、聚氧乙烯月桂基醚、聚氧乙烯烷基醚等縫系；聚氧乙稀油酸醋、聚惫7祕 ^ 09眾氧乙烯二硬脂酸酯、山梨糖醇 if月桂酸酉旨、山梨糖醇針單硬脂酸醋、山梨糖醇酐單油酸醋、山梨糖醇酐倍半油酸醋、聚氧乙稀單油酸醋、聚氧乙婦硬脂酸酯等醋系；2,4,7,9，甲基_5_癸炔'7_二醇、二甲基冰辛炔_3,6_二醇、3,5_二甲基]_己炔_3_醇等乙炔二醇（醇）系；曰信化學公司製商品名Surfyn〇li〇4、1〇5、82、 465 Olfine STG 等，聚二醇醚系（例如：sigma aldrich 公司製之Tergltol 15-S-7等）等。上述墨水調製劑分別可單獨使用或混合使用。本發明之墨水組成物’能夠經由以任意順序來將上述各成分混合、授拌而獲得。所得之墨水組成物，可依期望而使用膜濾,器等進行過濾，以去除夾雜物。此外，為了將彩度低且無色調之中性且高品質的黑色色相微調整成更期望的色相之目的等，本發明之墨水組成物’係除了上述色素⑴、色素（11)、色素⑽、色素（ιν)以外亦可在不損害由本發明所得之功效之範圍内，包含具 63 201237111 有各種色相之其他色素。此時’能夠混合使用下述色素：具有其他色相之黑色 (例如：C.I. Acid Black 1、C.I. Direct Black 22、C.I. Direct Black 19 等）；和橙色（例如：C.I· Direct Orange 17、C.I. Direct Orange 39、C.I. Direct Orange 49 等）、棕色、緋紅色（例如：C_I. Direct Red 89 等）、紅色（例如：c.I. Direct Red 62、C.I. Direct Red 75、C.I· Direct Red 79、C.I. Direct Red 84、C.I. Direct Red 225、C.I. Direct Red 226、C.I. Acid Red 249、C.I· Acid Red 254 等）、洋紅色（例如 c.I. Direct Red 227 等）、紫色、藍色、海軍藍色、綠色、青藍色（cyan)(例如： C.I. Direct Blue 199 > C.I. Acid Blue 9 ^ C.I. Acid Blue 249 等）、其他色的色素。本發明之墨水組成物，能夠在各種領域中使用’較適於書寫用水性墨水、水性印刷墨水、f訊記錄墨水等，以作為喷墨記錄用墨水使用特佳，適合用於後述之本發明之喷墨記錄方法中。以下說明本發明之噴墨記錄方法。本發明之喷墨記錄方法係使用本發明之墨水組成物作為墨水，使該墨水之墨水滴因應記錄訊號來喷出並使其附著在被記錄㈣，藉此進行記錄1行記錄時所使用之墨水噴嘴等係無特別限制’能夠因應目的而適當選擇。例如：利用靜電吸引麗電元件的振動壓力力脈衝方式）；將電子該記錄方法能夠採用習知方法，力使墨水喷出之電荷控制方式；利用之應需喷印（drop 〇n-demand)方式（塵 64 201237111 訊號轉換成聲束（一stie beam)來對墨水照射，而利射壓力使墨水噴出之聲波喷墨方式；將墨水加熱形成j .後’利用所產生之壓力之熱噴墨、亦即Bubble Jet(註冊商標）方式等。巧再者，喷墨記錄方法中亦包含下述方式：將稱為墨水之墨水中之色素濃度（色素含量）低的墨水，以來大量射出之方式；使用色相實質上相同且墨水中之濃度不同的複數種墨水來改良畫質之方式；以及使用無辛透明的墨水之方式等。 ‘、本發明之著色體，為藉由本發明之墨水組成物所之物質，以藉由使用喷墨印表機之喷墨記錄方法並藉發明之墨水組成物所著色之被記錄材料為佳。能夠著色之被記錄材料係無特別限制，可舉例薄膜等資訊傳遞用片材；纖維和布（纖維素、耐論、羊毛皮革1色器用基材等，其中，以資訊傳遞用片材為資2遞用片材以經進行表面處理為佳，具體而言以於、我、δ成紙、薄膜等基材設置有墨水接受層為佳接受層係藉由下述方法來設置，例如··使陽離子系聚人物含浸於上述基材中、或將陪雜；人^ 糸聚口物 4將陽離子Μ合物㈣於上述基材 =二多孔質氧…氧化紹溶膠、特殊陶£等能夠洛二Γ之色素之無機微粒子’與聚乙烯醇和聚乙浠口比疋：水性聚合物一起塗佈於前述基材表面之方法樣的設置有墨水接受層者，通常稱為嗔墨專用紙、 65 201237111 喷墨專用薄膜、光澤紙、或光澤薄臈等。上述資訊傳遞用片材中，特別是表面塗佈有多孔性白 • &無機物之片材，係由於表面光澤度高，並且_水性亦優 .異，故特別適於記錄相片圖像。然而，已知記錄在此等資況傳遞用片材之圖像，會因臭氧氣而使變/褪色情形變嚴重。然而’本發明之墨水組成物’係由於耐臭氧氣性優異，故在這樣的被記錄材料進行喷墨記錄時亦發揮較大的功效。作為如上所述之表面塗佈有多孔性白色無機物之片材’具代表性的市售物之一例可舉例如：Can〇n(股）製商品名.專業相片紙（Professional Ph〇t〇 Paper)、超級相片紙 (Super Photo Paper)、光澤G〇ld、及粗面相片紙（μ_抑⑽丫ΟΜθ NH (6h2)2 ho3s' is a water-soluble yellow dye of the pigment (IV), and a conventionally known water-soluble yellow dye of the preferred structure represented by the above formula (10) can be easily obtained from the market. The method described in Patent Document 4 is obtained. The pigment, the coloring matter (II), the coloring matter, and the salt of the coloring matter (IV) used in the ink composition of the present invention are salts with inorganic cations or organic cations. In the #, the salt formed with the inorganic cation may, for example, be a metal salt, an alkaline earth metal salt or an ammonium salt. The lithium salt 'sodium salt, a salt, and a salt are preferred. On the other hand, the salt formed by the organic cation is, for example, a salt formed by the quaternary ammonium represented by the following formula (19), but is not limited thereto. Further, free acids, tautomers thereof, and mixtures of the various salts thereof. The following mixture can be used. *'', σ, for example, a mixture of a sodium salt and a salt; a free acid and a sodium salt; a sigma, a lithium salt, a sodium salt, and an ammonium sleeping mixture. In some cases, the physical property value such as solubility may be determined by the type of the salt; the mixture may be obtained by appropriately selecting the type of the salt as needed or by changing the ratio when the complex b or the like is included. The physical properties of z1 ^ - N + 'Z2 23 (19) Z are independently expressed in the above formula (19), z1, z2, z3, not 55 201237111 hydrogen atom; from alkyl, hydroxyalkyl, and hydroxyalkane The group consisting of oxyalkyl groups gives the selected group ' and at least one of them represents a group other than a hydrogen atom. • Specific examples of the alkyl group of Z, Z2, Z3, and Z4 in the above formula (19) include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and secondary butyl group. Specific examples of the hydroxyalkyl group, such as a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, and the like, may be mentioned. A hydroxy (C1 to C4) alkyl group such as 2-hydroxybutyl. Specific examples of the hydroxyalkoxyalkyl group include a hydroxyethoxymethyl group, a 2-hydroxyethoxyethyl group, a 3-hydroxyethoxypropyl group, a 2-hydroxyethoxypropyl group, and a 4-hydroxyethyl group. A hydroxy (C1 to C4) alkoxy (C1 to C4) alkyl group such as oxybutyl group, 3-hydroxyethoxybutyl group or 2-hydroxyethoxybutyl group. Among these, hydroxyethoxy~C4)alkyl is preferred. Particularly preferred are: hydrogen atom; methyl; hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl Equivalent hydroxy (C1~C4) alkyl; hydroxyethoxy fluorenyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2 hydroxyethoxypropyl, 4-hydroxyethoxy A hydroxyethoxy (C1 to C4) alkyl group such as a butyl group, a 3-hydroxyethoxybutyl group or a 2-hydroxyethoxybutyl group. Among the preferred compounds represented by the above formula (19), specific examples of the combination of Z1, Z2, Z3 and Z4 are shown in Table 19 below. 56 201237111 [Table 19] Compound No. Z1 Ζ2 Z3 Z4 1-1 Η CH3 CH3 CH3 1-2 CH3 CH3 CH3 CH3 1-3 Η -C2H40H -C2H40H -C2H40H 1-4 CH3 -C2H40H -C2H40H -C2H40H 1-5 Η -CH2CH(0H)CH3 -CH2CH(0H)CH3 -CH2CH(0H)CH3 1-6 CH3 -CH2CH(OH)CH3 -CH2CH(0H) CH3 -CH2CH(0H)CH3 1-7 Η -C2H40H H -C2H40H 1-8 CH3 -C2H40H H -C2H40H 1-9 Η - CH2CH(OH)CH3 H -CH2CH(OH)CH3 1-10 CH3 -CH2CH(OH)CH3 H - CH2CH(OH)CH3 1-11 CH3 -C2H40H CH3 -C2H40H 1-12 CH3 -CH2CH(0H)CH3CH3 -CH2CH(0H)CH3 The ink composition of the present invention will be described below. The ink composition of the present invention contains a pigment (I), a pigment (II), or a pigment (ΠΙ) and a pigment (IV) as needed, and can color a material composed of cellulose. Further, it is also possible to color a material having a carboxyguanamine bond, and it can be widely used for materials such as leather, fabric, and paper. When the synthesis reaction of each of the dye (I), the dye (Π), the dye (III), and the dye (IV) is carried out, the respective reaction liquids after the final step can be directly used for producing the ink composition of the present invention. However, it is also possible to separate the respective dyes by mixing the respective dyes in the following manner to prepare an ink composition: first, the reaction liquid containing the respective dyes is separately dried, for example, spray-dried; and sodium chloride or gas is added thereto. An inorganic salt such as potassium, calcium chloride or sodium sulfate is used for salting out; acidification is carried out by adding a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid; or the above salting out is combined with acid precipitation to carry out acid precipitation, etc. . The ink composition of the present invention contains the coloring matter (I) and the coloring matter (II) as the color. In addition, in order to obtain more remarkable effects, the pigment (ΙΠ) and the pigment (IV) are contained as needed. The dye (1), the dye (II), and the dye (III) may each be a single dye within a range satisfying the above specific conditions, or may be a mixture of a plurality of dyes. Further, the pigment (1¥) is a compound having 1 to 2 azo groups in the i molecule and is a water-soluble yellow dye. Therefore, in the ink composition of the present invention, at least two or more kinds of pigments are blended, and four or more kinds of pigments are blended as needed. In the total mass of the pigment contained in the ink composition of the present invention, the ratio of the pigment (1) is 50 to 90% by mass, preferably 50 to 8 % by mass, and the ratio of the pigment (Π) is! ~10% by mass, preferably 1 to 8 mass%. When the pigment (III) and/or the pigment (IV) are formulated, the ratio of the pigment (πι) is 5 to mass^, preferably 5 to 15%, and the ratio of the pigment (IV) is 4 to 20% by mass. 4 to 15% by mass is preferred. Further, the total content of the pigment (1), the pigment (ι), and the pigment (m) and the pigment (IV) when necessary is usually % by mass of the enamel relative to the total mass of the ink composition, and is 1 to 10% by mass. Preferably, it is preferably 2 to 8 mass%. The ink composition of the present invention may further comprise a water-soluble organic solvent such as 〇30% by mass, an ink preparation agent such as 〇2 to 2% by mass, and the balance being water. For the purpose of improving the stability of storage, the ink composition of the present invention is preferably ΡΗ5 ηηη, preferably ρΗ7〜ί〇. Further, the surface tension of the ink composition is preferably 25 to 7 G mN/m, more preferably 25 to 6 q (10). Further, the viscosity of the ink composition is preferably 3 〇 mPa·s or less, preferably 2 〇 mPa·s or less. The pH of the ink composition of the present invention; the surface tension can be appropriately adjusted by adjusting the pH and the surfactant as described later: 58 201237111 The ink composition of the present invention is a pigment (1), a pigment (ι), and a pigment. (m) and the pigment is dissolved in water or a water-soluble organic solvent (organic: agent capable of mixing with water) and is added to the ink preparation agent as needed. When the ink composition is used as the ink for ink recording, it is preferable that the content of the inorganic impurities in the coloring matter (1), the coloring matter (9), the coloring matter, and the coloring matter (IV) contained in the ink composition of the present invention is small. The inorganic impurities are: a vapor of a metal cation (for example, sodium chloride), a sulfate of a metal cation (for example, sodium sulfate), and the like. The basis of the content of the inorganic impurities is about 1% by mass or less based on the total mass of the dye. The lower limit is the detection limit of the analysis machine, that is, the mass%. When producing a pigment having less inorganic impurities, the desalting treatment may be carried out only by the following method. For example, by a method of reverse osmosis membrane, in a mixed solvent of a solvent such as methanol (C1 to C4) and water, After the dried product of the dye or the wet cake is stirred, the precipitate is separated by filtration and dried, and the inorganic impurities are exchange-adsorbed by using an ion exchange resin. Specific examples of the water-soluble organic solvent that can be used in the preparation of the ink composition include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, and the like. (C1~C4) alkanol; N, carboxamide, such as diamine, N,N-dimercaptoacetamide; 2-pyrrolidone, 2, ketone, N-methyl N is more than an amidoxime such as acridine·2-ketone; 丨, 3-dimethyl-salt-bit 2', I3-dimercaptohexahydrocarcinoma. Cyclic ureas such as quinone-2-one; ketones such as propyl hydrazine, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or keto alcohols such as tetrahydrofuran, dioxane, etc. Cyclic ether; ethylene glycol, 12-propanol, 1,3-propanediol, 1>2•butanediol, 1>4-butanediol, 16-hexane 2 201237111 alcohol, diethylene glycol, triethyl Glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiethanol (thiGdigiy, dithiodiethanol, etc., two C2~C6 extended base units, polycondensation or polyalkylene glycol Or sulphur B: alcohols such as glycerol, hexamethylene 1,3,6-triol (triol); ethylene glycol single shout, ethylene glycol monoethyl test, ^ ethylene glycol monomethyl ether , diethylene glycol monoethyl ether: diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether monoethyl ether early ethyl ether and other polyols (C1 ~ C4) An alkyl ether; ruthenium (tetra), dimethylsulfoxime, etc. These organic solvents may be used singly or in combination of two or more. In this case, isopropanol, hydrazine, methyl group to ratio Slightly biting ketone, glycerin, and butyl carbitol are preferred. When the ink composition of the present invention is used, examples of the ink preparation which can be suitably used include, for example, an antiseptic and antifungal agent, a bismuth adjusting agent, a nip inhibitor, a rust preventive, a water-soluble ultraviolet absorbing agent, a water-soluble polymer compound, and a dyeing agent. The Jk oxidizing agent, the surfactant, etc. are explained. The ink preparation agents are described below. Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, mercaptopyridine, an oxide steel salt, and p-benzoquinone. Acid B, U benzopyrene _3_ ketone U, 2-benzisothiaz〇lin_3 〇ne) and its salts. The preservative may, for example, be an organic sulfur system, an organic nitrogen sulfur system, an organic functional system, an arylsulfone system, an iodopropargyl group, a haloalkylthio group, a nitrile system, a pyridine or a carpet-based group. Benzene benzothiazole, isothlazoUne, dithiol, pyridine oxide nitropropane, organotin, phenol, quaternary ammonium, triazine , thio D well 201237111 (thiazine), anthraquinone (anUide), adamantane, dithiocarbamate, bromoindanone, bromoacetate, inorganic salt, etc. Compound. Specific examples of the organic dentate-based compound include, for example, sodium pentasodium phenolate, and specific examples of the bite oxide compound are, for example, 2% mercaptopyridine oxide sodium salt, and specific examples of the isothiazoline-based compound include, for example:丨, I stupid isothiazol-3-one, 2-n-octyl-4-isothiazoline-3-one, 5-gas-2-iso-4-isothiazolin-3-one, 5-chloro- 2-mercapto-4-isothiazoline·3__magnesium chloride, 5_gas-2-methyl-4-isothiazoline_3_one calcium chloride, 2-methyl_4-isothiazoline_3_ ketone gas Calcium and so on. Specific examples of the other antiseptic and antifungal agent include anhydrous sodium acetate, sodium sorbate, sodium benzoate, or Pr. XelRTM GXL (S) or Proxel RTM XL 2 (S#, manufactured by Arch Chemicals Co., Ltd. In this specification, 'superscript' "RTM" means a registered trademark. A pH adjuster is used to control the pH of the ink to, for example, 5 to 丨丨 without adversely affecting the prepared ink. Any substance can be used, and specific examples thereof include an alkanolamine such as diethanolamine, triethanolamine or N-methyldiethanolamine; and a hydroxide of an alkali metal such as lithium hydroxide, sodium hydroxide or potassium hydroxide; Ammonium hydroxide (ammonia water); alkali metal carbonate such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate or potassium carbonate; alkali metal salt of organic acid such as sodium citrate or potassium acetate; inorganic base such as disodium hydrogen phosphate; The reagent may, for example, be disodium edetate, sodium nitrotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenediaminepentaacetate, sodium pyrimidine diacetate or the like. Examples are: acidic sulfites, thio Sodium sulphate, sulphur 61 201237111 pentaerythritol tetranitrate, ammonium nitrite glycolate, dicyclohexylammonium nitrite diisopropylhexylammonate, etc. The indigo ultraviolet green absorber may, for example, be as defined below. a benzophenone-based compound, a benzotriazine-based compound, a salicylic acid-based compound, a cinnamic acid-based compound, and a ternary compound. The polyvinyl alcohol and the cellulose-derived water-soluble polymer compound may, for example, be a biological or polyamine. A polyimine, etc. The caprolactam, the ethyl carbonate, and the urinary pigment dissolving agent are, for example, a phenol, etc. The antioxidant can use various organic-based and metal-compound-based anti-viscerants. Examples of the agent may, for example, be a hydrogen group, an oxo phenol, a dialkoxy phenol, a phenol, an aniline, an amine, an indane, a chromane, or an alkane. Examples of the surfactant include an anionic surfactant, a cationic surfactant, and a nonionic surfactant. Examples of the anionic surfactant include, for example, an alkanesulfonic acid. Salt, alkyl carboxylate, alpha-olefin sulfonate Polyalkyl alkyl ether acetate, N-decylamino acid and its salt, N-mercaptopurine taurate, alkyl sulfate polyoxyalkyl ether sulfate, alkane Sulphate polyoxyethylene alkyl ether sulphate, rosin acid soap, castor oil barium sulfate, lauryl sulfate, sulphuric acid phthalate, hospital based acid ester, aryl sulfonic acid Salt, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, monooctyl borosilicate, etc. Examples of cationic surfactants include, for example, 2-vinylpyridine derivative 62 201237111 Biological, poly(4-vinylpyridine) derivatives, etc. Examples of the amphoteric surfactants include, for example, lauryl dimethylaminoacetic acid beet test, 2-alkylaminomethyl group via ethyl ethyl group, and butterfly Salt beet test, coconut oil, lysine, urethane, acetic acid, sugar beet test, polyoctyl polyamine ethylglycine, or imidazoline derivative. Examples of the nonionic surfactant include, for example, polyoxyethylene phenyl phenyl mystery, polyoxyethylene octyl phenyl (10) 'polyoxyethyl 4 phenyl group, polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene alkyl ether and other sewing systems; polyoxyethylene oleic acid vinegar, polypyrene 7 secret ^ 09 oxyethylene distearate, sorbitol if lauric acid, sorbitol needle Vinegar monostearic acid vinegar, sorbitan monooleic acid vinegar, sorbitan sesquioleic acid vinegar, polyoxyethylene monooleic acid vinegar, polyoxymethylene stearate, etc.; 2, 4, 7,9, acetylene diol such as methyl _5_decyne '7-diol, dimethyl ice acetylene _3,6-diol, 3,5-dimethyl]-hexyne _3-alcohol (Alcohol); trade name of Surfyn Chemical Co., Ltd., Surfyn〇li〇4, 1〇5, 82, 465 Olfine STG, etc., polyglycol ether system (for example: Sigmagald Co., Ltd., Tergltol 15-S-7, etc.) Wait. The above ink preparation agents may be used singly or in combination. The ink composition 'of the present invention' can be obtained by mixing and mixing the above components in an arbitrary order. The obtained ink composition can be filtered by a membrane filter or the like as desired to remove inclusions. Further, in order to finely adjust the black hue of low chroma and no hue neutrality and high quality to a more desirable hue, the ink composition of the present invention is selected from the above-mentioned pigment (1), pigment (11), and pigment (10). In addition to the pigment (ιν), other pigments having various hue of 63 201237111 may be contained within a range that does not impair the effects obtained by the present invention. At this time, 'the following pigments can be mixed: black with other hue (for example: CI Acid Black 1, CI Direct Black 22, CI Direct Black 19, etc.); and orange (for example: CI· Direct Orange 17, CI Direct Orange 39) , CI Direct Orange 49, etc.), brown, magenta (eg C_I. Direct Red 89, etc.), red (eg cI Direct Red 62, CI Direct Red 75, CI· Direct Red 79, CI Direct Red 84, CI Direct Red 225, CI Direct Red 226, CI Acid Red 249, CI· Acid Red 254, etc.), magenta (eg cI Direct Red 227, etc.), purple, blue, navy blue, green, cyan (cyan) For example: CI Direct Blue 199 > CI Acid Blue 9 ^ CI Acid Blue 249, etc.), other color pigments. The ink composition of the present invention can be used in various fields, such as a water-based ink suitable for writing, an aqueous printing ink, an ink for recording ink, etc., and is particularly preferably used as an ink for inkjet recording, and is suitable for use in the invention described later. In the inkjet recording method. The ink jet recording method of the present invention will be described below. In the ink jet recording method of the present invention, the ink composition of the present invention is used as an ink, and the ink droplets of the ink are ejected by the recording signal and attached to the recorded (four), thereby being used for recording one line of recording. There is no particular limitation on the ink nozzle or the like, which can be appropriately selected depending on the purpose. For example, the use of electrostatic attraction to the vibrating pressure force pulse mode of the electric component; the electronic recording method can adopt the conventional method, the force control mode for the ink to be ejected; and the use of the drop 〇n-demand The method (dust 64 201237111 signal is converted into a beam (stie beam) to illuminate the ink, and the pressure of the jet causes the ink to be ejected by the sonic inkjet method; the ink is heated to form j. After the 'hot ink using the generated pressure In other words, the Bubble Jet (registered trademark) method, etc., in addition, the inkjet recording method also includes the following method: a method of injecting a large amount of ink having a low pigment concentration (pigment content) in an ink called ink a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations in the ink; and a method of using a non-clear transparent ink, etc. ', the color body of the present invention is an ink composition by the present invention The substance is preferably a material to be recorded which is colored by an ink jet recording method using an ink jet printer and which is colored by the ink composition of the invention. The material to be recorded is not particularly limited, and examples thereof include a sheet for information transmission such as a film, a fiber and a cloth (a substrate for cellulose, a cotton, a leather, and a monochromator, and the sheet for information transmission is used as a sheet for information transfer. Preferably, the material is subjected to surface treatment, and specifically, an ink receiving layer is provided on a substrate such as δ, paper, or film. Preferably, the receiving layer is provided by the following method, for example, cation polymerization The person is impregnated in the above-mentioned substrate, or will be accommodating; the human 糸糸 4 4 will be a cationic conjugate (4) in the above substrate = two porous oxygen ... oxidized sol, special Tao, etc. The inorganic fine particles of the pigment are compared with the polyvinyl alcohol and the polyethylene bismuth: the aqueous polymer is coated on the surface of the substrate together with the ink receiving layer, which is generally called the ink special paper, 65 201237111 inkjet Special film, glossy paper, or glossy enamel, etc. Among the above-mentioned sheets for information transmission, especially the surface coated with porous white & inorganic materials, the surface gloss is high, and _ water is also excellent. Different, so it is especially suitable A photo image is recorded. However, it is known that the image recorded on the sheet for the transfer of these conditions is deteriorated due to ozone gas. However, the ink composition of the present invention is resistant to ozone gas. Since it is excellent in the inkjet recording of such a recorded material, it also exerts a large effect. As an example of a commercially available product of a sheet coated with a porous white inorganic material as described above, a typical example can be exemplified. Such as: Can〇n (share) system name. Professional Photo Paper (Professional Ph〇t〇 Paper), Super Photo Paper (Super Photo Paper), Gloss G〇ld, and rough photo paper (μ_ (10)

Paw Seik〇EpS〇n(股）製商品名：相片用紙Crispia(高光澤）、相片用紙（光澤）、粗面相片紙（ph〇t〇MattePa㈣；曰本HP(股）製商品名：高級相片用紙（Adv謝^ ph〇t〇光澤剛FILM(股）製商品名：晝彩相片精加工 Pro等。再者，當然亦能夠使用普通紙。在以本發明之噴墨記錄方法來在資訊傳遞用片材等被記錄材料進行記錄時，只要以下述方式進行即可，例如：將包含上述墨水組成物之容器設置在嘴墨印表機的預定位置，並以一般記錄方法來在被記錄材料進行記錄。本發明之喷墨記錄方法亦能夠將本發明之墨水組成物與下述墨水組成物併用，例如：習知的洋紅色、青藍色、黃色；以及因應需要之綠色、藍色(或紫色）、紅色(或橙色） 66 201237111 等各色的墨水組成物。各色的墨水組成物係以下述方式用於進行喷墨記錄：注入各自之容器中，並將該各容器與包含本發明之里水組成物之容器同樣地裝填在喷墨印表機的預定位置。* 本發明之墨水組成物中所含之色素，係容易合成且且此外由於對以水作為主要成分之介質之溶解性高，且水溶性優異，故在製造墨水組成物之過程中藉由膜遽器來過濾之過濾性良好。 ° 製之：：該化合物之墨水組成物、或由該墨水組成物所調 ’水’保存時之安定性和喷出安定性均優異。換言之，本發明之墨水組成物，係長時間保存後出、物性變化、色相變化等…… 體析燹化等，而儲存安定性良好❶ 此外’包含該色素之墨水組成物，適合用於作為噴墨 ==用、書寫用具用。當以本發明之墨水組成物來在喷墨專用紙進行記錄時，在進曲隹進仃^辰色印刷及淡色印刷時之任一 =不均呈現無色調之中性的黑〜灰色，並且色相不會因使;同而變化。此外，記錄圖像之列印濃度非常高 =高濃度溶液’該圓像亦不會發生泛金光現象，並且 =生、耐水性等各種牢固性均優異，特別是耐光性及财臭氧氣性均優異。此外，與包含洋紅 # ^ ^ u 、·色色素、青藍色色素及黃色色素之卉他墨水組成物併用，即亦能夠用热並、s 匕夠進行全彩的噴墨記錄，當然性優異。；9、紙’該喷墨記錄的各種牢固性優異且保存 67 201237111 如上所述，本發明之墨水組成物係極有用於作為噴墨記錄用黑色墨水。 [實施例] 以下藉由實施例來具體說明本發明，但本發明並不受下述實施例任何限定。本文中，只要未特別記載，「份」及「％」即為質量基準。只要未特別說明，各合成反應、晶析等操作，均係在攪拌下進行。在下述各式中，磺基、羧基等酸性官能基係以游離酸之形態來表示。合成反應中之pH值及反應溫度，均係表示反應系統内之測定值。此外’所合成之化合物之最大吸收波長（Xmax)，為在 pH 7〜8之水溶液中進行測定，在實施例中，所測定之化合物係記载其測定值。再者，下述實施例中所合成之偶氮化合物，均係對水顯示100 g/L以上之溶解性。 (A)染料之合成 [實施例1] (步驟1) 使氯-3-硝基苯胺51.8份溶於N-甲基-2-吨\各咬鋼 60·〇份中’並費時約15分鐘在其中滴入乙酸酐35.2份。 68 201237111 滴入後，在40〜50°C使其反應2小時後，將反應液添加至水400份中。在室溫搜拌30分鐘後，過濾所析出之固體’ 並在漏斗上以水1 00份將所得之固體洗淨，並分取、乾燥’ 而獲得下述式（20)所示之化合物63.0份。Paw Seik〇EpS〇n (stock) product name: photo paper Crispia (high gloss), photo paper (gloss), matte photo paper (ph〇t〇MattePa (four); 曰本HP (share) system name: advanced photo Paper (Adv Xie ^ ph〇t 〇 Glossy just FILM (stock) product name: enamel photo finishing Pro, etc. Further, of course, plain paper can also be used. In the inkjet recording method of the present invention in the information transmission When recording is performed by a recording material such as a sheet, it may be carried out in the following manner, for example, a container containing the above ink composition is placed at a predetermined position of the ink jet printer, and the material to be recorded is recorded by a general recording method. Recording. The ink jet recording method of the present invention can also use the ink composition of the present invention in combination with the following ink compositions, for example, conventional magenta, cyan, yellow; and green, blue (as needed) Or purple), red (or orange) 66 201237111 and other ink compositions. The ink compositions of each color are used for inkjet recording in the following manner: into each container, and the containers are The container containing the water composition of the present invention is similarly loaded at a predetermined position of the ink jet printer. * The pigment contained in the ink composition of the present invention is easily synthesized and, in addition, due to the use of water as a main component The medium has high solubility and excellent water solubility, so that the filtration property by the membrane buffer is good in the process of producing the ink composition. °: The ink composition of the compound or the ink composition The stability and the spray stability of the adjusted 'water' are excellent. In other words, the ink composition of the present invention is stored for a long time, changes in physical properties, change in hue, etc., etc., and storage stability Good performance ❶ In addition, the ink composition containing the pigment is suitable for use as an inkjet==for writing utensils. When the ink composition of the present invention is used for recording on inkjet special paper,仃^ Chen color printing and light color printing any = unevenness presents a toneless neutral black ~ gray, and the hue does not change; the same, the print density of the recorded image is very high = In the high-concentration solution, the round image does not cause bronzing, and it is excellent in various solidities such as greenness and water resistance, and is excellent in light resistance and ozone gas. In addition, it contains magenta # ^ ^ u , ·Color pigment, cyan pigment and yellow pigment. The ink composition can be used together, that is, it can also be used for full-color inkjet recording with heat and s. It is excellent in nature. 9. Paper's inkjet recording Excellent in various kinds of solidity and preservation 67 201237111 As described above, the ink composition of the present invention is extremely useful as a black ink for inkjet recording. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the present invention It is not limited to the following examples. In this document, "parts" and "%" are the quality standards unless otherwise specified. Unless otherwise specified, each of the synthesis reaction, crystallization, and the like is carried out under stirring. In the following formulas, an acidic functional group such as a sulfo group or a carboxyl group is represented by a form of a free acid. The pH value and the reaction temperature in the synthesis reaction are the measured values in the reaction system. Further, the maximum absorption wavelength (Xmax) of the compound to be synthesized is measured in an aqueous solution of pH 7 to 8, and in the examples, the measured compounds are described as measured values. Further, the azo compounds synthesized in the following examples all showed solubility in water of 100 g/L or more. (A) Synthesis of Dye [Example 1] (Step 1) 51.8 parts of chloro-3-nitroaniline was dissolved in N-methyl-2-ton\each bite steel 60 〇 part and took about 15 minutes 35.2 parts of acetic anhydride was added dropwise thereto. 68 201237111 After the dropwise addition, the reaction mixture was allowed to react at 40 to 50 ° C for 2 hours, and then the reaction liquid was added to 400 parts of water. After mixing for 30 minutes at room temperature, the precipitated solid was filtered, and the obtained solid was washed with 100 parts of water on a funnel, and separated and dried to obtain a compound 63.0 represented by the following formula (20). Share.

(步驟2) 使上述實施例1(步驟1)中所得之式（20)所示之化合物 42.9份溶於N-甲基-2-吡咯啶酮ι15.〇份中，並在其中添加 3-巯基丙磺酸鈉40.9份及碳酸鉀29.0份。添加後，加熱至 130〜140°C，並在130〜1401使其反應2小時❶再添加3- 酼基丙磺酸鈉3.6份後，在130〜i4〇〇c使其反應1小時。冷卻至60°C後’將反應液添加至2·丙醇700份中，並冷卻至室溫後，過濾分取所得之固體。使所得之濕濾餅溶於水 300份中後，經由添加35%鹽酸來調整成pH3.0〜4〇後，以氣化鈉來進行鹽析，並過濾分取所析出之固體，而獲得下述式（21)所示之化合物之濕濾餅2〇5·3份。(Step 2) 42.9 parts of the compound of the formula (20) obtained in the above Example 1 (Step 1) was dissolved in N-methyl-2-pyrrolidone ι 15. 〇 part, and 3- 40.9 parts of sodium mercaptopropanesulfonate and 29.0 parts of potassium carbonate. After the addition, the mixture was heated to 130 to 140 ° C, and reacted at 130 to 1401 for 2 hours, and then added with 3.6 parts of sodium 3-mercaptopropanesulfonate, and then reacted at 130 to 4 ° C for 1 hour. After cooling to 60 ° C, the reaction mixture was added to 700 parts of 2-propanol, and after cooling to room temperature, the obtained solid was separated by filtration. After the obtained wet cake was dissolved in 300 parts of water, the pH was adjusted to 3.0 to 4 Torr by adding 35% hydrochloric acid, and then salting out was carried out by vaporizing sodium, and the precipitated solid was separated by filtration. The wet cake of the compound represented by the following formula (21) was 2 〇 5·3 parts.

(步驟3) 在水150份中添加上述實施例丨（步驟2)中所得之式pi) 所示之化合物之濕濾餅1〇2 6份、活性碳i " 切及無水氯 69 201237111 化鐵（111)0.4份’並加熱至60°C後，費時約30分鐘滴入80 % 水合肼（hydrazine hydrate)15.9 份。加熱至 90°C 後，在 90°C使其反應1.5小時》冷卻至40°C後，藉由過渡來去除不溶物’並將滤液冷卻至室溫。經由添加5 〇 %硫酸來調整成pH 1.0〜1.5後’過濾分取所析出之固體，而獲得下述式 (22)所示之化合物之濕濾餅62.3份。(Step 3) 1 part of a wet cake of the compound of the formula pi) obtained in the above Example 丨 (Step 2) was added to 150 parts of water, activated carbon i " cut and anhydrous chlorine 69 201237111 After iron (111) 0.4 parts' and heated to 60 ° C, it took about 30 minutes to drip in an amount of 15.9 parts of 80% hydrazine hydrate. After heating to 90 ° C, the reaction was allowed to proceed at 90 ° C for 1.5 hours. After cooling to 40 ° C, the insoluble matter was removed by the transition and the filtrate was cooled to room temperature. After the solid was precipitated by adding 5 〇% sulfuric acid to adjust the pH to 1.0 to 1.5, 62.3 parts of the wet cake of the compound represented by the following formula (22) was obtained.

(步驟4) 在水40份中添加下述式（23)所示之5-胺基-2-氣苯磺酸12.6份後’經由添加25%氫氧化鈉水溶液來調整成pH 4.0〜5.0 ’而獲得水溶液。添加35%鹽酸25份後，添加4〇 %亞硝酸鈉水溶液12.6份，並使其反應約30分鐘。在其中添加胺磺酸1.5份，並攪拌5分鐘，而獲得重氮反應液。另一方面’在水200份中添加上述實施例丨（步驟3)中所得之式（22)所不之化合物之濕濾餅32 4份後，經由添加 25%氫氧化鈉水溶液來調整成pH 4 〇〜5 〇，而獲得水溶液°費時約5分鐘在上述中所得之重氮反應液中滴入此水 /合液。滴入後，一面經由添加丨5 %碳酸鈉水溶液來將pH 保持在2.0〜2.5，一面使其反應3小時後，經由添加氣化鈉來進行鹽析。過濾分取所析出之固體，而獲得下述式（24) 所示之化合物之濕濾餅3丨5份。 70 201237111(Step 4) After adding 12.6 parts of 5-amino-2-benzenesulfonic acid represented by the following formula (23) to 40 parts of water, 'adjusted to pH 4.0 to 5.0 by adding 25% aqueous sodium hydroxide solution' And an aqueous solution is obtained. After adding 25 parts of 35% hydrochloric acid, 12.6 parts of a 4 % aqueous sodium nitrite solution was added, and the reaction was allowed to proceed for about 30 minutes. 1.5 parts of an amine sulfonic acid was added thereto and stirred for 5 minutes to obtain a diazo reaction liquid. On the other hand, after adding 4 parts of the wet cake of the compound of the formula (22) obtained in the above Example 丨 (Step 3) to 200 parts of water, the pH was adjusted to pH by adding a 25% aqueous sodium hydroxide solution. 4 〇~5 〇, and obtaining the aqueous solution ° takes about 5 minutes to drip the water/liquid mixture into the diazonium reaction liquid obtained above. After the dropwise addition, the reaction was carried out for 3 hours while maintaining the pH at 2.0 to 2.5 by adding a 5% aqueous sodium carbonate solution, and then salting out was carried out by adding sodium carbonate. The precipitated solid was separated by filtration to obtain 3 丨 5 parts of a wet cake of the compound represented by the following formula (24). 70 201237111

H〇3S >H (24) (步驟5) 所得之式（24) 經由添加25%氫氧化鈉水得水溶液。添加3 5 %鹽酸在水40份中添加上述實施例丨（步驟中所示之化合物之濕濾餅總量後，經由添加25 溶液來調整成pH 6.0〜7.0，而獲得水溶液。； 24.8份後，添加40%亞硝酸鈉水溶液9 8份，並使其反應約30分鐘。在其中添加胺磺酸2〇份，並攪拌5分鐘，而獲得重氮反應液。另一方面’在水250份中添加上述實施例以步驟3)中所得之式（22)所示之化合物之濕濾餅3〇 8份後，經由添加 25%氫氧化鈉水溶液來調整成pH 4.0〜5.0，而獲得水溶液。費時約5分鐘在上述中所得之重氮反應液中滴入此水 /谷液。滴入後’ 一面經由添加1 5 %碳酸納水溶液來將pH 保持在2 · 〇〜2.5 ’ 一面使其反應3小時後，經由添加氣化納來進行鹽析。過濾分取所析出之固體，而獲得下述式（25) 所示之化合物之濕濾餅90份。H〇3S > H (24) (Step 5) The obtained formula (24) was obtained by adding 25% aqueous sodium hydroxide. Adding 35% hydrochloric acid to 40 parts of water, the above example 丨 (the total amount of the wet cake of the compound shown in the step is adjusted to pH 6.0 to 7.0 by adding 25 solution to obtain an aqueous solution; 24.8 parts after Adding 8 8 parts of a 40% aqueous solution of sodium nitrite and reacting it for about 30 minutes, adding 2 parts of amine sulfonic acid thereto, and stirring for 5 minutes to obtain a diazo reaction liquid. On the other hand, '250 parts in water To the above, the wet cake of the compound of the formula (22) obtained in the above step 3) was added in an amount of 3 〇 8 parts, and then adjusted to pH 4.0 to 5.0 by adding a 25% aqueous sodium hydroxide solution to obtain an aqueous solution. This water/cold solution was added dropwise to the diazonium reaction liquid obtained above in about 5 minutes. After the dropwise addition, the reaction was carried out for 3 hours while maintaining the pH at 2 · 〇 to 2.5 Å by adding a 15 % aqueous sodium carbonate solution, and then salting out was carried out by adding gasified sodium. The precipitated solid was separated by filtration to obtain 90 parts of a wet cake of the compound of the formula (25) below.

(步驟6> 71 201237111 在水250份中添加上述實施例i(步驟4)中所得之式㈣所示之化合物之濕濾餅45份，並攪拌使其溶解。添加W %鹽酸16.5份後’添加4G%亞石肖酸納水溶液份並授拌約30分鐘。在其中添加胺續酸2 ()份並授拌$分鐘，而獲得重氮反應液。另方面，在水6〇份中添加由日本特開2004_083492 號公報中所記載之方法所得之下述式（26)之化合物5.5份後，經由添加25%氫氧化鈉水溶液來調整成pH4 5〜5 5 , 而獲得水溶液。費時約5分鐘在上述t所得之重氮反應液中滴入此水溶液。滴人後’―面經由添加15%碳酸納水溶液來將pH保持在2.0〜3.〇,—面使其反應3小時。經由添 ^ 15%碳酸鈉水溶液來將pH調整成4 5後，添加甲醇35〇份。過濾分取所析出之固體，而獲得下述式(27)所示之化合物之濕濾餅96.6份。(Step 6 > 71 201237111 45 parts of the wet cake of the compound of the formula (IV) obtained in the above Example i (Step 4) was added to 250 parts of water, and stirred to dissolve. After adding 16.5 parts of W% hydrochloric acid' Add 4G% aqueous solution of succinate and mix for about 30 minutes, add 2 parts of the amine acid and mix for $ minutes to obtain the diazo reaction solution. On the other hand, add 6 parts of water. After 5.5 parts of the compound of the following formula (26) obtained by the method described in JP-A-2004-083492, the solution was adjusted to pH 4 5 to 5 5 by adding a 25% aqueous sodium hydroxide solution to obtain an aqueous solution. The aqueous solution was added dropwise to the diazonium reaction solution obtained in the above t. After the dropwise addition, the pH was maintained at 2.0 to 3. by adding a 15% aqueous sodium carbonate solution, and the reaction was carried out for 3 hours. After adjusting the pH to 45 by a 15% aqueous sodium carbonate solution, 35 parts of methanol was added, and the precipitated solid was separated by filtration to obtain 96.6 parts of a wet cake of the compound represented by the following formula (27).

Cl ho3s' so3hCl ho3s' so3h

•n=n^-n=n >-nh V-NH h3c h3c (步驟7) 在水170份中添加上述實施例丨（步驟6)中所得之式（27) 所示之化合物之濕濾餅32.2份’並攪拌使其溶解。添加35 %鹽酸5.2份後，添加40%亞硝酸鈉水溶液15份，並攪 72 201237111 拌約30刀鐘。在其中添加胺續酸1.0份，並授拌5分鐘，而獲得重氮反應液。另一方面，在水60份中加入由專利文獻1中所記載之方法所得之下述式（28)所示之化合物2.2份後，加入25%• n=n^-n=n >-nh V-NH h3c h3c (Step 7) The wet filter of the compound of the formula (27) obtained in the above Example 丨 (Step 6) is added to 170 parts of water. 32.2 parts of the cake was stirred and dissolved. After adding 5.2 parts of 35% hydrochloric acid, 15 parts of a 40% aqueous solution of sodium nitrite was added, and stirred at 72 201237111 for about 30 knives. 1.0 part of an amine acid was added thereto, and the mixture was stirred for 5 minutes to obtain a diazo reaction liquid. On the other hand, after adding 2.2 parts of the compound represented by the following formula (28) obtained by the method described in Patent Document 1 to 60 parts of water, 25% is added.

氫氧化鈉水溶液調整成pH75〜8 5，而獲得水溶液。在U 費夺、’句3 0分鐘在此水溶液中滴入上述中所得之重The aqueous sodium hydroxide solution was adjusted to pH 75 to 85 to obtain an aqueous solution. In U, the weight of the above is dropped into the aqueous solution in the sentence of 30 minutes.

氮反應液。此時，一面加入碳酸鈉水溶液將反應液之pH '、夺在7.5 8.5，並維持15〜30C及調整pH，一面再使其反應2小時。在反應液中加入氯化鈉進行鹽析後，過渡分離所析出之固體，而獲得濕濾餅29 5份。使所得之濕濾餅溶於水100份中，並以35%鹽酸將pH調整成7 〇〜7 5後，添加甲醇8 〇份’並過濾分取所析出之固體。使所得之濕黄餅再次溶於水60份中後，添加甲醇90份。過濾分離所析出之固體並乾燥，藉此以鈉鹽之形式獲得本發 ( __ 々〈下述式 )所示之化合物6.3份。Xmax : 589 nm。Nitrogen reaction solution. At this time, the pH of the reaction mixture was adjusted to 7.5 8.5 while maintaining an aqueous solution of sodium carbonate, and the reaction was carried out for 2 hours while maintaining the pH at 15 to 30 C. After sodium chloride was added to the reaction mixture for salting out, the precipitated solid was separated by a transition to obtain 29 parts of a wet cake. The obtained wet cake was dissolved in 100 parts of water, and the pH was adjusted to 7 〇 to 7 5 with 35% hydrochloric acid, and then 8 parts of methanol was added and the precipitated solid was separated by filtration. After the obtained wet yellow cake was dissolved again in 60 parts of water, 90 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 6.3 parts of the compound of the present invention ( __ 々 < the following formula) in the form of a sodium salt. Xmax: 589 nm.

73 201237111 [實施例2] 在水140份中添加實施们中所得之式（μ)所示之化勿3伤之納鹽、及氯化經14份並檀拌，而獲得水溶液。添加2_丙醇彻份’並㈣分取所析出之固體，而獲得濕慮餅再人在水1 5G份中添加所得之濕遽餅及氯化鐘^2 5 份並攪拌，而獲得水溶液。添加孓丙#㈣份，並過濾分取所析出之㈣’而獲得濕濾餅。使所得之濕㈣溶於水 8〇份中，並加入2_丙醇15〇份後，過濾分離所析出之固體，而獲得濕濾餅。使再次獲得之濕濾餅溶於水4〇份中，並加入2-丙醇100份後，過濾分離所析出之固體並乾燥，藉此以鈉鹽與鋰鹽之混合鹽之形式獲得本發明之上述式（29)所示之化合物4.5份。Xmax : 586 nm。 [實施例3] (步驟1) 使2-曱基-6-硝基苯胺15.2份溶於曱醇3〇〇份中。將所得之溶液移至高壓釜中後，加入5%Pd/碳2.0份，並在2〇〜30°C在0.2〜0.5 MPa之氫氣加壓下使其反應直到停止吸收氫氣為止後，在20〜30°C再持續反應3〇分鐘。過濾分離觸媒（5% Pd/碳）’藉此獲得包含下述式（3〇)所示之化合物之溶液（渡液）。 rrV-NH2 h3co 人Άνη2 (30) (步驟2) 74 201237111 在實施例3(步驟〇中所得之包含: 之溶液200份中加入氰乙酸曱酯13 〇分鐘後，將曱醇減壓濃縮，並加入水] 酸納調整成PH 7.〇〜7.5後，過濾分离燥，藉此獲得下述式（31)所示之化合物〇中所得之包含式（30)所示 (乙酸曱酯13.0份，並使 I縮’並加入水1〇〇份，鋏之化合物酸曱醋13.0份’並使其回流3〇 ’並加入水100份’然後加入碳後’過濾'分離所析出之固體並乾示之化合物8.3份。73 201237111 [Example 2] An aqueous solution was obtained by adding the sodium salt of the formula (μ) obtained in the formula (μ) obtained in the example, and 14 parts of the chlorinated mixture to the sandalwood. Add 2_propanol fraction ' and (4) to separate the precipitated solid to obtain a wet cake, and then add the obtained wet cake and chlorination clock to 25 parts of water and stir it to obtain an aqueous solution. . The crucible #(四) portion was added, and the precipitated (four)' was separated by filtration to obtain a wet cake. The obtained wet (iv) was dissolved in 8 parts of water, and after adding 15 parts of 2-propanol, the precipitated solid was separated by filtration to obtain a wet cake. The wet cake obtained again is dissolved in 4 parts of water, and after adding 100 parts of 2-propanol, the precipitated solid is separated by filtration and dried, thereby obtaining the present invention in the form of a mixed salt of a sodium salt and a lithium salt. 4.5 parts of the compound represented by the above formula (29). Xmax: 586 nm. [Example 3] (Step 1) 15.2 parts of 2-mercapto-6-nitroaniline was dissolved in 3 parts of decyl alcohol. After the obtained solution was transferred to an autoclave, 2.0 parts of 5% Pd/carbon was added, and the reaction was carried out under a pressure of 0.2 to 0.5 MPa of hydrogen at 2 to 30 ° C until the hydrogen absorption was stopped until 20 Continue to react for 3 minutes at ~30 °C. The catalyst (5% Pd/carbon) was filtered to thereby obtain a solution (such as a liquid) containing a compound represented by the following formula (3). rrV-NH2 h3co human Άνη2 (30) (Step 2) 74 201237111 After adding decyl cyanoacetate to the 200 parts of the solution obtained in the step 3 (Step 〇), the sterol was concentrated under reduced pressure, and After adding sodium hydroxide to pH 7.〇~7.5, the mixture was separated by filtration to obtain a compound represented by the following formula (31), which was obtained by the formula (30) (13.0 parts of decyl acetate). And make I shrink and add 1 part of water, simmer the compound bismuth vinegar 13.0 parts 'and make it reflux 3 〇 ' and add water 100 parts ' then add carbon and then 'filter' separate the precipitated solid and dry The compound was 8.3 parts.

(步驟3) 在乙醇100份中加入上述式（3 1}所示之化合物83份、 28%甲醇鈉12.0份、及乙醯乙酸曱酯7 2份，並使其回流 30分鐘後’將乙醇減壓濃縮，並加入水1 〇〇份，然後加入 35%鹽酸調整成pH 7.0〜7.5後，過濾分離所析出之固體並乾燥，藉此獲得下述式（3 2)所示之化合物11 · 1份。所得之下述式（32)所示之化合物為混合物，係在b或c取代有曱氧基之化合物之混合物。(Step 3) 83 parts of the compound represented by the above formula (3 1}, 12.0 parts of 28% sodium methoxide, and 72 parts of decyl acetate acetate were added to 100 parts of ethanol, and refluxed for 30 minutes. The organic layer was concentrated under reduced pressure, and 1 part of water was added, and then adjusted to pH 7.0 to 7.5 by adding 35% hydrochloric acid, and the precipitated solid was separated by filtration and dried to obtain a compound 11 represented by the following formula (3 2). 1 part. The obtained compound represented by the following formula (32) is a mixture which is a mixture of compounds in which b or c is substituted with an oxiranyl group.

(步驟4) 在5〜10°C在8%發煙硫酸77份中緩緩添加上述式（32) 所示之化合物5.6份後，在5〜1(TC使其反應i·5小時°費時約10分鐘在冰水150份中滴入反應液，並在65〜70°C 攪拌30分鐘後，過濾分離所析出之固體’藉此獲得下述式 (33)所示之化合物之濕濾餅24.4份。下述式（33)所示之化 75 201237111 合物為混合物，係甲氧基在b的位置，磺基的取代位置為或d，或疋甲氧基在c的位置，續基的取代位置為a、 b或d之化合物之混合物。(Step 4) After gradually adding 5.6 parts of the compound represented by the above formula (32) to 77 parts of 8% fuming sulfuric acid at 5 to 10 ° C, the reaction time is 5 to 1 (TC is made to react for 5 hours). The reaction liquid was added dropwise to 150 parts of ice water for about 10 minutes, and after stirring at 65 to 70 ° C for 30 minutes, the precipitated solid was separated by filtration, whereby a wet cake of the compound represented by the following formula (33) was obtained. 24.4 parts. The compound 75 201237111 represented by the following formula (33) is a mixture, the methoxy group is at the position of b, the substitution position of the sulfo group is or d, or the position of the methoxy group at the position of c, the contig A mixture of compounds having a substitution position of a, b or d.

(步驟5) 除了在上述實施例U步驟7)中，使用實施例3(步驟4) 中所付之式（33)所示之化合物之濕遽餅7.2份’取代式（28) 所不之化合物2.2份以外，其餘與實施例1 (步驟7)同樣進行，而以鈉鹽之形式獲得本發明之下述式（34)所示之化合物6.3份。所得之色素為由2〜6種化合物所構成之混合色，該些化合物係在下述式（34)中，f氧基在b的位置，磺基的取代位置為a、c或d;或是曱氧基在c的位置，磺基的取代位置為a、b或d之化合物。(Step 5) Except that in the above-mentioned Example U, step 7), 7.2 parts of the wet cake of the compound represented by the formula (33) which was paid in Example 3 (Step 4) was substituted for the formula (28). Except for 2.2 parts of the compound, the same procedure as in Example 1 (Step 7) was carried out, and 6.3 parts of the compound represented by the following formula (34) of the present invention was obtained as a sodium salt. The obtained pigment is a mixed color composed of 2 to 6 kinds of compounds, and the compounds are in the following formula (34), wherein the f-oxy group is at the position b, and the sulfo group is substituted at a, c or d; The methoxy group is at the position of c, and the sulfo group is substituted with a compound of a, b or d.

[實施例戶1除了在上述實施例2令，使用上述實施例3(步驟。中所得之式(34)所示之化合物之鈉鹽88份，取代式㈣所示之化合物之鈉鹽6.3份以外，其餘與實施例2同樣進行不 76 201237111 而以鈉鹽與鋰鹽之混合鹽之形式獲得本發明之上述式（34) 所示之化合物4.5份。Xmax : 592 nm。 [實施例5] (步驟1) 使2-甲基-6-硝基苯胺15.2份溶於甲醇300份中。將所得之溶液移至面壓爸中後，加入5%Pd/碳2.0份，並在搜拌下在20〜30°C在0.2〜0.5 MPa之氫氣加壓下使其反應直到停止吸收氫氣為止後，在20〜30°C再持續反應3〇分鐘。過濾分離觸媒（5% Pd/碳）’藉此獲得包含下述式（3 5)所示之化合物之溶液（濾液）。 CH,[Example 1 except that in the above Example 2, 88 parts of the sodium salt of the compound represented by the formula (34) obtained in the above Example 3 (step) was substituted for the 6.3 part of the sodium salt of the compound represented by the formula (IV). In the same manner as in Example 2, except for the combination of the sodium salt and the lithium salt, 4.5 parts of the compound of the above formula (34) of the present invention was obtained in the same manner as in Example 2, and Xmax: 592 nm. [Example 5] (Step 1) 15.2 parts of 2-methyl-6-nitroaniline was dissolved in 300 parts of methanol. After the resulting solution was transferred to a dough pressure, 2.0 parts of 5% Pd/carbon was added, and the mixture was mixed. After reacting at 20 to 30 ° C under a hydrogen pressure of 0.2 to 0.5 MPa until the hydrogen gas absorption is stopped, the reaction is continued for another 3 minutes at 20 to 30 ° C. The catalyst for separation by filtration (5% Pd/carbon) 'Thereby obtaining a solution (filtrate) containing a compound represented by the following formula (3 5). CH,

(35) (步驟2) 在包含上述式（35)所示之化合物之溶液200份中加入下述式（36)所示之化合物13·〇份’並在攪拌下使其回流3〇分鐘後’將反應液減壓濃縮，並加入水1 5〇份，然後加入碳酸納調整成pH 7.0〜7.5。過濾分離所析出之固體並乾燥’藉此獲得下述式（37)所示之化合物8.4份。再者，了述式（36)所示之化合物係以專利文獻5中所記載之方 β。 NH-HC1 古獲付。 NCsA0Ch3 (36)(35) (Step 2) A compound 13 〇 part ' represented by the following formula (36) is added to 200 parts of the solution containing the compound represented by the above formula (35), and refluxed for 3 minutes after stirring. 'The reaction solution was concentrated under reduced pressure, and 15 parts of water was added, and then sodium carbonate was added to adjust to pH 7.0 to 7.5. The precipitated solid was separated by filtration and dried to thereby obtain 8.4 parts of the compound represented by the following formula (37). Further, the compound represented by the formula (36) is a square β described in Patent Document 5. NH-HC1 was paid in ancient times. NCsA0Ch3 (36)

(步驟3) 77 201237111 在乙醇100份中加入上建式（37)所不之化入4 28%曱醇鈉12.3份、及乙。物8.4伤、及乙醯乙酸曱酯7.4份， 3〇分鐘後，將乙醇減壓濃绐^ ^ 卫便其回流堅，辰縮，並加入水150份 35%鹽酸調整成pH7.〇〜 ·'、、後加入 /.5後，過濾分離所析出乾燥，藉此獲得下述式（38、所-入出之固體並 ()所不之化合物1 〇〇 ⑽所示之化合物係在a或d的位 H3Cv PN π τ 丞。(Step 3) 77 201237111 Into 100 parts of ethanol, 12.3 parts of 4 28% sodium decoxide and B were added to the above formula (37). 8.4 wounds, and 7.4 parts of acetoacetate acetate, after 3 minutes, the ethanol was decompressed and concentrated ^ ^ Wei to its reflux, shrink, and added 150 parts of water 35% hydrochloric acid to adjust to pH 7. 〇 ~ After the addition of /.5, the filtration separation is carried out to dry, thereby obtaining a compound represented by the following formula (38, the solid which is introduced and the compound which is not contained in the compound 1 〇〇 (10) is a or d. The bit H3Cv PN π τ 丞.

(38) (步驟4) 在5〜10以3%發煙硫酸1〇2份中緩緩添加上述式 ⑽所示之化合物5.0份後，在小時約Η)分鐘在冰水24〇份中滴人反應液後，過“離所析出之固體，藉此獲得包含下述式（39)所示之化合物之濕渡餅 14.7份。下述式（39)所示之化合物為下述任一化合物^甲基在a的位置，績基的取代位置為c;或是？基在以位置，磺基的取代位置為b。 h3c cn(38) (Step 4) After adding 5.0 parts of the compound represented by the above formula (10) to 5 to 10 parts of 3% fuming sulfuric acid in 5 to 10, it is dropped in 24 parts of ice water at about Η) minutes. After the human reaction liquid, 14.7 parts of the wet cake containing the compound represented by the following formula (39) is obtained from the solid which is precipitated. The compound represented by the following formula (39) is any of the following compounds. ^Methyl at the position of a, the substitution position of the base is c; or the base is at the position, and the position of the sulfo is b. h3c cn

(39) (步驟5) 除了在上述實施例i(步驟7)中，使用實施例5(步驟句中所得之式（39)所示之化合物之關餅"份，取代式⑽ 78 201237111 所示之化合物2.2份以外’其餘與實施们(步驟行，而以鈉鹽之形式獲得本發明之下述式（4〇)所仆進物6.0份。所得之g音合所侍之色素為由2〜6種化合物所構成之素，該化合㈣在下述式_中，甲氧基纟b的位置^ 基的取代位置為a、c或d;或是甲氧基在c的位置，：磺的取代位置為a、b或d。 ^基(39) (Step 5) In addition to the above Example i (Step 7), the use of the compound of the formula (39) obtained in the step ("39") is used instead of the formula (10) 78 201237111 In addition to the 2.2 parts of the compound, the remainder and the implementer (steps, and in the form of a sodium salt, 6.0 parts of the servant of the following formula (4〇) of the present invention are obtained. The obtained dye of the g-synthesis is 2 a compound composed of ~6 kinds of compounds, wherein the compound (4) is in the following formula: the position of the methoxy oxime b is substituted with a, c or d; or the position of the methoxy group at c: sulfonate The substitution position is a, b or d.

[實施例6] (40) 除了在上述實施例2中，使用上述實施例5(步驟5)中所得之式（40)所示之化合物之鈉鹽8 8份，取代式（29)所八之化合物之鈉鹽6.3份以外，其餘與實施例2同樣進=不而以鈉鹽與鋰鹽之混合鹽之形式獲得本發明之上述式（4〇) 所示之化合物4.0份。Xmax : 590 nm。 L貫施例7J (步驟1) 在水250份中添加上述實施例丨（步驟4)中所得之式（24) 所示之化合物之濕濾餅45份，並攪拌使其溶解。添加μ %鹽酸16.5份後’添加4 0 %亞硝酸鈉水、玄饬4 〜冷收4.7份，並撥拌約30分鐘。在其中添加胺磺酸2.0份，诉捭扯c J 业規袢5分鐘而獲得重氮反應液。 201237111 另方面在水6〇份中添加由日本特開2〇〇4_〇83492 號公報中所記載之方法所得之下述式⑷）之化合物5.8份後，經由添加25%氫氧化鈉水溶液來調整成PH4.5〜5.5, 而獲得水溶液。費時約s八# + , 1 , • 5刀鐘在上述中所得之重氮反應液 t ^ Hn滴人後’—面經由添加碳酸納水溶液來將PH保持在2.0〜3.0, 一面使其反應3小時。經由添加15%碳酸納水溶液來將PH調整心.5後，添加甲醇350 份。過據分取所析出之固體，而獲得下述式(42)所示之化合物之濕濾餅94.0份。[Example 6] (40) In the above Example 2, 8 8 parts of the sodium salt of the compound represented by the formula (40) obtained in the above Example 5 (Step 5) was used instead of the formula (29) The same applies to Example 2 except for the 6.3 parts of the sodium salt of the compound. In the form of a mixed salt of a sodium salt and a lithium salt, 4.0 parts of the compound of the above formula (4〇) of the present invention is obtained. Xmax : 590 nm. L Example 7J (Step 1) 45 parts of the wet cake of the compound of the formula (24) obtained in the above Example 丨 (Step 4) was added to 250 parts of water, and stirred to dissolve. After adding 16.5 parts of μ% hydrochloric acid, '40% sodium nitrite water, ginseng 4~ 4.7 parts cold was added, and the mixture was stirred for about 30 minutes. 2.0 parts of the amine sulfonic acid was added thereto, and the diazonium reaction liquid was obtained by licking for 5 minutes. In addition, 5.8 parts of the compound of the following formula (4)) obtained by the method described in JP-A No. 4, No. 83492 is added to a water of 6 parts, and then a 25% sodium hydroxide aqueous solution is added thereto. Adjust to pH 4.5 to 5.5 to obtain an aqueous solution.费时约 s8#, 1, 1 , • 5 knives in the above-mentioned diazonium reaction solution t ^ Hn after the drop - the surface is maintained at 2.0 to 3.0 by adding an aqueous solution of sodium carbonate, while reacting 3 hour. After the pH was adjusted to 5 by adding a 15% aqueous sodium carbonate solution, 350 parts of methanol was added. The precipitated solid was fractionated to obtain 94.0 parts of a wet cake of the compound of the formula (42) below.

so3h h3c>'NH HaC (42) (步驟2) /水170份中添加上述實施例他驟υ中所得之式（42 ^之化合物之濕渡餅31·3份，並搜拌使其溶解。添加h 酸5·2份後’添加4〇%亞硝酸鈉水溶液L5份，並授拌約30分鐘。在其中诉中添加胺％酸U份’錢拌5分鐘，而獲得重氮反應液。另一方面’在水60份中加入由 + 1 寻利文獻1中所記載之方法所得之上述式⑽心之化伪傻，加入25% 氫氧化鈉水溶液調整成pH 7.5〜 '5而獲付水溶液。在15 80 201237111 〜30°C費時約30分鐘在此水溶液中滴入上述中所得之重So3h h3c> 'NH HaC (42) (Step 2) / 170 parts of water were added to the above formula (31. 3 parts of the wet cake of the compound of 42 ^, and mixed to dissolve. After adding 2.5 parts of h acid, '5 parts of 4% sodium nitrite aqueous solution was added, and the mixture was stirred for about 30 minutes. In the middle, the amine % acid U was added for 5 minutes to obtain a diazo reaction liquid. On the other hand, the above formula (10) obtained by the method described in the document 1 of the above-mentioned document 1 was added to 60 parts of water, and the solution was adjusted to a pH of 7.5 to '5 by adding a 25% aqueous sodium hydroxide solution. Aqueous solution. The weight of the above obtained in the aqueous solution is about 30 minutes at 15 80 201237111 to 30 ° C.

氮反應液。此時，一面加入碳酸鈉水溶液將反應液之pH 保持在7.5〜8.5’並維持15〜3(rc及調整pH，一面再使其反應2小時。在反應液中加人氯化鈉進行鹽析後，過據分離所析出之固體，而獲得濕遽餅3〇.〇份。使所得之濕遽^ 溶於水1〇〇份中，並以35%鹽酸將pH調整成7〇〜7 5後，添加甲醇80份’並過遽分取所析出之固體。使所得之濕據餅再次溶於水60份中後，添加甲醇9〇份。過濾分離所：出之固體並乾燥，藉此以納鹽之形式獲得下述式（43)所示之化合物6.0份。 μNitrogen reaction solution. At this time, the pH of the reaction solution was maintained at 7.5 to 8.5 Å while maintaining the pH of 15 to 3 (rc and pH adjustment, and the reaction was further carried out for 2 hours while adding a sodium carbonate aqueous solution. The sodium chloride was added to the reaction solution for salting out. Then, the solid which precipitated was separated, and the wet cake was obtained, and the obtained wet cake was dissolved in 1 part of water, and the pH was adjusted to 7〇~7 5 with 35% hydrochloric acid. Thereafter, 80 parts of methanol was added and the precipitated solid was separated and the resulting wet cake was dissolved in 60 parts of water again, and then 9 parts of methanol was added. The solid was separated by filtration and dried. 6.0 parts of the compound represented by the following formula (43) is obtained in the form of a sodium salt.

[實施例8] 在水140份中添加實施例7中所得之式⑷)所示之合物6.0份之鈉鹽、及氣化經14份並搅拌，而獲得水：添加2-丙醇400份，並過渡分取所析出之固體，而：滤钟。再次在7"5°份中添加所得之濕濾餅及氣化二:5 份並而獲得水溶液。添加Μ醇350份，並:\ 取所析出之《，而獲得㈣餅。使所得之濕逯 8”二’並加入2_丙醇15。份後，過攄分離所析出二、體，而獲得濕錢。使再錢得之誠趣於水刃Τ，並加 201237111 入2-丙醇1 〇〇份後’過遽分離所析出之固體並乾燥，藉此以鈉鹽與鋰鹽之混合鹽之形式獲得本發明之上述式（43)所 • 示之化合物4.3份。Xmax : 590 nm。 [實施例9] 除了在上述實施例i(步驟乃中，使用實施例3(步驟4) 中所得之式（33)所Μ化合物之職餅72份，取代式⑽ 所示之化合物2.2份以外’其餘與實施例丨（步驟7)同樣進灯，而以鈉鹽之形式獲得本發明之下述式（44)所示之化合物5.6份。所得之色素為由2〜6種化合物所構成之混合色素，該化合物係在下述式（44)中，甲氧基& b的位置，續基的取代位置為a、。或d;或是甲氧基在c的位置，磺基的取代位置為a、b或d。[Example 8] 6.0 parts of the sodium salt of the compound of the formula (4)) obtained in Example 7 was added to 140 parts of water, and 14 parts of the gasification was stirred and stirred to obtain water: 2-propanol 400 was added. And transfer the solids separated, and: filter clock. The obtained wet cake was again added in 7 " 5 parts and gasified two: 5 parts to obtain an aqueous solution. Add 350 parts of sterol, and: \ take the precipitated ", and get the (four) cake. After the obtained wet mash is 8"2' and added to the 2-propanol 15 part, the bismuth separation separates the body and obtains the wet money, so that the money is more interesting to the water blade, and added 201237111 After the 2-propanol 1 is aliquoted, the precipitated solid is separated and dried, whereby 4.3 parts of the compound of the above formula (43) of the present invention is obtained as a mixed salt of a sodium salt and a lithium salt. Xmax: 590 nm. [Example 9] In addition to the above-mentioned Example i (Step: 72 parts of the compound of the compound of the formula (33) obtained in Example 3 (Step 4), instead of the formula (10) The compound was further subjected to the same procedure as in Example 丨 (Step 7), and 5.6 parts of the compound of the following formula (44) of the present invention was obtained in the form of a sodium salt. The obtained pigment was from 2 to 6 a mixed dye composed of a compound, wherein the compound is in the following formula (44), the position of the methoxy group and the b group, the substitution position of the contig is a, or d; or the position of the methoxy group at the c, The substitution position of the sulfo group is a, b or d.

[實施例10] 除了在上述實施例7中，使用上述實施例9中所得之式（44)所不之化合物之鈉鹽5 6份， & ^ @ 狀代式（43)所示之化合物之鈉1 6.0份以外，其餘與實施例？㈣進行，而以納鹽與經鹽之混合鹽之形式獲得本發明之上述式⑽所示之化合物 4.0 份。Xmax : 597 nm。 82 201237111 使上述實施例1〜1 〇中所得之色素溶於離子交換水中’而分別調製水中溶有5%之色素之溶液。將所得之溶液置入密閉容器中，並使其靜置於60°c之恆溫恆濕機中i 週’但未發生色素分解。 (B)墨水之調製經由將上述實施例4、1 0中所得之各染料與下述表2〇中所記載之各成分一起混合，而獲得黑色的本發明之墨水組成物後，使用0.45 μηι之膜濾器濾除夾雜物後，將所得之墨水組成物分別作為實施例丨丨及12。以下將所得之墨水組成物稱為「墨水」。此外，表2 〇中，色素、累色染料之列係經虛線分割成上下2列，上列中記載實施例、比較例中之化合物之式編號，τ列中記载所使用之份數。此外，在表20中，實施例4、1〇之化合物係記載為式（34)、 (44) ’但由於進料實施例之操作，故實際上為鈉鹽與裡鹽之混合鹽。此外’記號「_」係意指不包含屬於左欄所記載之物。此外’水係使用離子交換^在調製墨水時，係以氫氧化鋰將墨水之阳調整成pH7〜9，然後經由加入 1〇〇份。再者’下述表20中之界離子交換水來使總量成為面活性劑’係使用日信化學股份有限公司冑商品名[Example 10] Except that in the above Example 7, the sodium salt of the compound of the formula (44) obtained in the above Example 9 was used, and the compound represented by the formula (43) was used. The sodium other than 6.0 parts, the rest with the examples? (4) The present invention is carried out, and 4.0 parts of the compound of the above formula (10) of the present invention is obtained in the form of a mixed salt of a sodium salt and a salt. Xmax : 597 nm. 82 201237111 The pigments obtained in the above Examples 1 to 1 were dissolved in ion-exchanged water to prepare a solution in which 5% of the pigment was dissolved in water. The resulting solution was placed in a closed container and allowed to stand in a constant temperature and humidity machine at 60 ° C for 1 week but no photodegradation occurred. (B) Preparation of Ink After the respective dyes obtained in the above Examples 4 and 10 were mixed with the respective components described in the following Table 2 to obtain a black ink composition of the present invention, 0.45 μm was used. After the membrane filter was filtered to remove inclusions, the obtained ink compositions were designated as Examples 1 and 12, respectively. Hereinafter, the obtained ink composition will be referred to as "ink". Further, in Table 2, the coloring matter and the coloring dye are divided into upper and lower columns by a broken line, and the formula numbers of the compounds in the examples and the comparative examples are shown in the above column, and the number of parts used in the τ column is described. Further, in Table 20, the compounds of Examples 4 and 1 are described as Formulas (34) and (44)'. However, due to the operation of the feed examples, they are actually a mixed salt of a sodium salt and a lye salt. Further, the 'marker '_' means that it does not include the items listed in the left column. In addition, when the water is used for ion-exchange, the ink is adjusted to pH 7 to 9 with lithium hydroxide, and then added by one part. Further, 'the ion exchange water in the following Table 20 is used to make the total amount into a surfactant.'

Surfynol 104PG50 ° 經由將下述表20之各成分混合，而獲得比較例η 之墨水。再者，比較例用之墨水之調冑，係藉由與前述實施例之墨水之調製同樣的作業來進行。 [表 20] 83 201237111 00 鎵 i 1 > 1 1 i 1 1 翁· 1 | i 1 1 1 « 1 | s| 1 tA · . w I CO i 1 1 1 i 1 | i « 1 1 i 1 I t/3 ΙΑ 寸 CO c^a oo - CD t— Γ— g j 1 | wj 1 1 1 1 » 1 1 ] 1 i 1 1 1 J 1 i lo | c\^ i 1 1 t j 1 i I 1 1 j 1 i 1 1 1 j 1 to ΙΛ CO Ds3 CO c=> Ο t— c— g 1 1 wi I 1 1 t 1 1 1 1 1 1 CD Si 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 { t 1 j 1 1 j 1 1 j 1 1 j 1 tra LO CO Cv3 CO o c> Ο t«- r- o -ϋ «! i 1 1 1 i t 1 1 I 1 LO 您 1 » 1 1 1 1 \ 1 1 "'1 '" 1 1 1 1 1 m CO 〜CO i j i 1 i j i t f j 1 t i 1 i 1 i | i 1 LO LA 寸 e*i C^3 oo o • O ·—* Ο r* o o aJ w| 1 1 I 1 1 | 1 1 ! I 1 | 1 1 1 ^•1 呀1 t 1 » 1 < <»-s I oo» 1 1 1 1 1 1 呀丨对1 V»»» .1^ I CO — o | wjc=> w J c=> 1 I 1 c=> o ο LT3 Wj 1 1 «1 1 1 1 1 CO U /-N * 勺· I I 1 1 1 /—\ · LD ! y**s 1 00 ! 1 1 t • 1 1 oo co!. W I CO 1 1 I -js 1 1 I < ! i I LO ΙΑ 寸 eo CO o e=3 ο U3 C— o W| ( 1 Wj «j 1 1 ( 1 〇〇 I 1 1 1 J 1 i _ 1 \ | 1 i LO j C'r 1 1 1 » J 1 j 却丨寸 | i 1 1 1 J 1 il> Lf3 CO CNJ eo C3 Q C3 75.5 o ◦ -£ ! 1 1 1 Wi t 1 1 «i t 1 1 1 γΗ 1 1 1 j 1 1 1 1丨1 1 (15) 1.35 1 1 1 1 j 1 (4 5) 2,35 #>-N tol ΙΛ IT3 CO ¢0 〇 c=> LO tri g <·< -ϋ w! 1 t «! «! (Μ r—1 1 1 /-s | 1 « s! la m ΊΓά 1 1 /-N j 00 1 V 寸|7 、^» CO οΰ 1 « • i o o 1 I a· 'όΓδ! 1 | 1 • 1 | t 1 1ft ΙΛ 寸 eo CO o o ο LO Γ— g «! I I «! 1 < l < 1 r~i τ-Η 1 y-V I ^«Lft 1 S ! ΙΛ 1 二丨 ^ ' Lf3 1 /•V | 00-1Λ 1 1 LO 罢 Ag col^ w J eo «1° 1 1 ^ j 〇 ^ j o ill 1 1 ill LT3 U3 寸 CO c-a o d ο ΙΛ r— o K· «丨 1 I 1 犮 1 签 Ί r-*' 窩 /·—>» i—i > Jj s ϋ 蘅实 t- &- B S—✓ 漆銨 4W ΚΣΙ 铿 * ¥ <a) »K Ί ν§ 2： h κ3 岭 84 201237111 上述表 20 中 ’ D.R.80 為 c.I· Direct Red 80。上述表20中’式（15)所示之色素（III)，係對專利文獻 3中所s己載之合成例進行重複試驗而得。上述表20中，式（18)所示之色素（IV)，係對專利文獻 4中所記载之合成例進行重複試驗而得。 [比較例1] 使用國際公開第2007/077931號之實施例2中所揭示之色素，作為比較對象之黑色色素，而調製墨水，以此墨水作為比較例i之墨水。此等色素係經由對專利中所記載之合成法進行重複試驗而得。比較例〗之墨水中所使用之色素（45)及（46)之結構係如下述所示。Surfynol 104PG50 ° The ink of Comparative Example η was obtained by mixing the components of Table 20 below. Further, the adjustment of the ink for the comparative example was carried out by the same operation as the preparation of the ink of the above-described embodiment. [Table 20] 83 201237111 00 Gallium i 1 > 1 1 i 1 1 Weng·1 | i 1 1 1 « 1 | s| 1 tA · . w I CO i 1 1 1 i 1 | i « 1 1 i 1 I t / 3 CO inch CO c^a oo - CD t - Γ - gj 1 | wj 1 1 1 1 » 1 1 ] 1 i 1 1 1 J 1 i lo | c\^ i 1 1 tj 1 i I 1 1 j 1 i 1 1 1 j 1 to ΙΛ CO Ds3 CO c=> Ο t— c— g 1 1 wi I 1 1 t 1 1 1 1 1 1 CD Si 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 { t 1 j 1 1 j 1 1 j 1 1 j 1 tra LO CO Cv3 CO o c> Ο t«- r- o -ϋ «! i 1 1 1 it 1 1 I 1 LO You 1 » 1 1 1 1 \ 1 1 "'1 '" 1 1 1 1 1 m CO ~CO iji 1 ijitfj 1 ti 1 i 1 i | i 1 LO LA inch e*i C^3 oo o • O ·— * Ο r* oo aJ w| 1 1 I 1 1 | 1 1 ! I 1 | 1 1 1 ^•1 呀1 t 1 » 1 <<»-s I oo» 1 1 1 1 1 1 1 V»»» .1^ I CO — o | wjc=> w J c=> 1 I 1 c=> o ο LT3 Wj 1 1 «1 1 1 1 1 CO U /-N * Spoon · II 1 1 1 /—\ · LD ! y**s 1 00 ! 1 1 t • 1 1 oo co!. WI CO 1 1 I -js 1 1 I < ! i I LO ΙΑ inch eo CO oe=3 ο U3 C— o W| ( 1 Wj «j 1 1 ( 1 〇〇I 1 1 1 J 1 i _ 1 \ | 1 i LO j C'r 1 1 1 » J 1 j but 丨 inch | i 1 1 1 J 1 il> Lf3 CO CNJ eo C3 Q C3 75.5 o ◦ -£ ! 1 1 1 Wi t 1 1 «it 1 1 1 γΗ 1 1 1 j 1 1 1 1丨1 1 (15) 1.35 1 1 1 1 j 1 (4 5) 2,35 #>-N tol ΙΛ IT3 CO ¢0 〇c=> LO tri g <·< -ϋ w! 1 t «! «! (Μ r—1 1 1 /-s | 1 « s! la m ΊΓά 1 1 /-N j 00 1 V inch|7 , ^» CO οΰ 1 « • ioo 1 I a· 'όΓδ! 1 | 1 • 1 | t 1 1ft ΙΛ inch eo CO oo ο LO Γ— g «! II «! 1 < l < 1 r~i τ-Η 1 yV I ^«Lft 1 S ! ΙΛ 1 二丨^ ' Lf3 1 /•V | 00-1Λ 1 1 LO Stop Ag col^ w J eo «1° 1 1 ^ j 〇^ jo ill 1 1 ill LT3 U3 inch CO Ca od ο ΙΛ r— o K· «丨1 I 1 犮1 sign Ί r-*' nest/·->» i-i > Jj s ϋ蘅 t t- &- B S-✓ lacquer ammonium 4W ΚΣΙ 铿 * ¥ <a) »K Ί ν§ 2: h κ3 岭 84 201237111 In the above table 20 ' D.R.80 is c.I· Direct Red 80. The dye (III) represented by the formula (15) in the above Table 20 was obtained by repeating the test of the synthesis example contained in Patent Document 3. In the above Table 20, the dye (IV) represented by the formula (18) was obtained by repeating the test of the synthesis examples described in Patent Document 4. [Comparative Example 1] The ink disclosed in Example 2 of International Publication No. 2007/077931 was used as a black pigment to be compared, and ink was prepared so that the ink was used as the ink of Comparative Example i. These pigments are obtained by repeating the test by the synthesis method described in the patent. The structures of the dyes (45) and (46) used in the ink of Comparative Example are as follows.

[比較例2] 使用日本特開2009-185 133號公示之色素，作為比較對象之黑色色素墨水作為比較例2之墨水。此等色素载之合成法進行重複試驗两得。比較句2009-185 133號公報之實施例i中所揭七較對象之黑色色素，而調製墨水，以此 2之墨水《此等色素係經由對專利中所記 6複試驗两得。比較例2之墨水中所使用 85 201237111 之色素（47)之結構係如 HOgS*[Comparative Example 2] A black pigment ink to be compared was used as the ink of Comparative Example 2, using the pigment disclosed in JP-A-2009-185 133. The synthesis method of these pigments was repeated for two trials. Comparative Example No. 2009-185 No. 133, the black pigment of the object is disclosed in the example i, and the ink is prepared, and the ink of the second embodiment is obtained by the two tests of the patent. The color of the pigment (47) used in the ink of Comparative Example 2 is as follows: HOgS*

n (47)n (47)

^~N=I S03H HaC" HOjS (C)喷墨記錄 so3h 公司製嘴墨印表 1及2進行噴墨使用上述中所得之墨水，使用canon 機商品名HXUS IP4⑽，在下述光澤紙記錄。光澤紙1 : Canon公司制水、·客从 . 先澤紙，商品名相片用紙澤 Pro[PT-101A420] Λ ^ 光澤紙2 ·· Canon公司製朵、、要铋念 :蛋Γ丨… Ί裂先澤紙’商品名相片用紙-光澤 Gold[GL-l〇lA41〇〇] 進行印刷時’係以能夠獲得⑽％、戰、咖、4〇义、20%、10%濃度之6階段的深淡層次（濃淡層次）之方式製作圖像圖案’而獲得遭黑色〜淡黑色的層次之記錄物’將此記錄物作為試驗片實施下述評估試驗。 (〇)記錄圖像之評估使用實施们1、12及比較例卜8之墨水而得之各記錄圖像’係測定試驗前後之圖像的濃度變化而進行評估。記錄圖像的濃度變化係藉由下述方式進行測定：使用 GRETAG-MACBETH公司製之測色機商品名叶咖〇咖，對試驗前之記錄圖像的反㈣度Dk值最接& 1〇之層次部刀進行測色。進行測定時，均係在下述條件下進行：濃度基準為 DIN(DeUtSChe Industrie Nomung C〇1〇ur System)、視 86 201237111 角2。、光源D65。耐臭氧痛、性試驗係在試驗前之反射濃度最接近1 .〇之層次部分進行幸仃牛固性試驗。具體的試驗方係如下所述。 (E)彩度試驗為了評估在光澤紙i 色相之品質，而評估彩度用上述測色系統測定CIL 算出。進行喷墨記錄而得之圖像之黑色值。評估彩度C*值時，係使之L*、a*、b*後，使用下述式 C* = (a*2+ b*2)1^ 試驗結果係以下述基準來進行評估。試驗結果係如表所示。C*值較小者（較接近〇者），係較接近無彩色且無色調之高品質的黑色，故較優異。〇：CT值未達8 △ : C*值為8以上且未達 X : C*值為1〇以上 (F)泛金光性評估為了評估在光澤紙1進行喷墨記錄而得之圖像之泛金光性，而使螢光燈的光在記錄圖像反射後，以肉眼來確認其反射光’藉此進行是否發生泛金光現象之評估。所得之記錄圖像宜不發生泛金光現象。結果係如表21所示。 A :在1 〇〇%深淡層次部分未發生泛金光現象。 B :僅在100%深淡層次部分發生泛金光現象。 C :在1 〇〇%及80%深淡層次部分發生泛金光現象。 D .在60%深淡層次部分或更低的深淡層次部分發生 87 201237111 泛金光現象。 [表 21]^~N=I S03H HaC" HOjS (C) Inkjet recording so3h Ink ink printing table 1 and 2 inkjet The ink obtained in the above was recorded using the canon machine name HXUS IP4 (10) on the following glossy paper. Glossy paper 1 : Canon company water, · Guest from. Zee paper, product name photo paper Pro [PT-101A420] Λ ^ Glossy paper 2 · Canon company making, mourning: egg tart... Ί Cracked Zeeze Paper 'Product Name Photo Paper - Gloss Gold[GL-l〇lA41〇〇] When printing, it is a 6-stage process that can obtain (10)%, war, coffee, 4%, 20%, 10% concentration. In the dark level (darkness level), an image pattern was created to obtain a recorded matter of a black to light black level. This recorded matter was subjected to the following evaluation test as a test piece. (〇) Evaluation of Recorded Images Each of the recorded images obtained by using the inks of the embodiments 1 and 12 and Comparative Example 8 was evaluated by measuring the change in the density of the images before and after the test. The change in the density of the recorded image was measured by the following method: using the color measuring machine product name of GRETAG-MACBETH Co., Ltd., the inverse (four) degree Dk value of the recorded image before the test was the best & 1 The knives of the knives are used for color measurement. The measurement was carried out under the following conditions: The concentration standard was DIN (DeUtSChe Industrie Nomung C〇1〇ur System), and 86 201237111 angle 2. , light source D65. The ozone-resistance and sex test were carried out before the test. The concentration of the reflection was closest to 1. The specific test methods are as follows. (E) Saturation test In order to evaluate the quality of the hue of the glossy paper i, the chroma was evaluated by the above colorimetric system. The black value of the image obtained by inkjet recording. When the chroma C* value is evaluated, the following formula C* = (a*2+ b*2)1^ is used after L*, a*, and b*, and the test results are evaluated based on the following criteria. The test results are shown in the table. Those with a smaller C* value (closer to the latter) are superior in color to a black color that is closer to achromatic and colorless. 〇: CT value is less than 8 △ : C* value is 8 or more and X is not reached: C* value is 1 or more (F) Panthroism evaluation To evaluate the image obtained by performing inkjet recording on glossy paper 1. The luminosity is made, and the light of the fluorescent lamp is reflected by the recorded image, and the reflected light is visually confirmed by the naked eye', thereby evaluating whether or not the bronzing phenomenon occurs. It is preferable that the recorded image obtained does not have a bronzing phenomenon. The results are shown in Table 21. A: There is no bronzing in the 1 〇〇% dark level. B: The phenomenon of bronzing occurs only in the 100% dark level. C: The phenomenon of bronzing occurs in the 1 〇〇% and 80% faint areas. D. In the 60% dark level or lower part of the dark level 87 201237111 Pan-Golden phenomenon. [Table 21]

(E)彩度 (F)泛金光性 C* 實施例11 〇 A 實施例12 〇 A A 比較例1 〇比較例2 Δ A 比較例3 〇 A 比較例4 〇 A 比較例5 X C 比較例6 X C 比較例7 X A 比較例8 X A 由表21之結果明顯可知，與比較例5〜8之墨水相比，各實施例之墨水的列印濃度更優異。此外，相對於比較例 5及6之墨水發生泛金光；見象，本發明之墨水係具有不發生泛金光現象之特徵。換言之，明顯可知，各實施例之墨水’能夠獲得無彩色且不發生泛金光現象之高品質的黑色圖像。 (G)耐臭氧氣性試驗使用實施例11〜12及比較例1〜6之墨水而得之各記錄圖像’係在印刷後自然乾燥24小時後，使用Suga試驗 88 201237111 機（股）公司製商品名臭氡耐候試驗機，在臭氧氣濃度40 ppm、濕度6〇% RH、溫度24 C之條件下將各試驗片故置8 小時。試驗結束後，使用上述測务檄推〜〗邑機進仃測色，而測定試驗刚後之色差（△ E)。再者’所得乡 t、巴差Λ £較指由臭氧氣所造成之變色較少，而表示耐* 思再者，下述計算式中，H性較優異。 ^ d ^ Δ b% v 暴露前後之L*、a*及b*之差值。为別係意指 ^E=(AL*2 + Aa*2+ Ab*2)1/2 ◎ : AE值為3.5以下〇.ΔΕ值為3.5以上且未達5.0 .△ Ε值為5.0以上且未達7.5 :△ Ε值為7.5以鬌(E) Saturation (F) Pan-gold luminescence C* Example 11 〇A Example 12 〇AA Comparison Example 1 〇Comparative Example 2 Δ A Comparative Example 3 〇A Comparative Example 4 〇A Comparative Example 5 XC Comparative Example 6 XC Comparative Example 7 XA Comparative Example 8 XA It is apparent from the results of Table 21 that the inks of the respective examples were more excellent in printing density than the inks of Comparative Examples 5 to 8. Further, bronzing was generated with respect to the inks of Comparative Examples 5 and 6; it is seen that the ink of the present invention has a feature that no bronzing phenomenon occurs. In other words, it is apparent that the ink of each embodiment can obtain a high-quality black image which is achromatic and does not cause bronzing. (G) Ozone gas resistance test Each of the recorded images obtained by using the inks of Examples 11 to 12 and Comparative Examples 1 to 6 was dried naturally for 24 hours after printing, and then used Suga Test 88 201237111 Machine Co., Ltd. The product name was skunk weathering tester, and each test piece was set to stand for 8 hours under the conditions of an ozone gas concentration of 40 ppm, a humidity of 6〇% RH, and a temperature of 24 C. After the end of the test, use the above test to push ~ 〗邑 machine to measure the color, and determine the color difference (△ E) immediately after the test. In addition, the income of the township t and the bark is less than that caused by ozone gas, and it means that the resistance is the same. ^ d ^ Δ b% v Difference between L*, a* and b* before and after exposure. For other purposes, ^E=(AL*2 + Aa*2+Ab*2)1/2 ◎ : AE value is 3.5 or less 〇.ΔΕ value is 3.5 or more and less than 5.0. △ Ε value is 5.0 or more and Less than 7.5: △ Ε is 7.5 鬌

89 201237111 由表22之結果明顯可知，與比較例1〜6之墨水相比，各實施例之墨水的耐臭氧氣性極為優異。換言之，明顯可知’耐臭氧氣性試驗後之色差（△ E)極小，而由臭氧氣所造成之變/褪色更少。此外，明顯可知，牢固性不會因媒介而顯者降低’而能夠獲得高品質的記錄圖像。 [產業上之可利用性] 於書寫用具等各種墨記錄用之黑色墨本發明之黑色墨水組成物係適合用記錄用之黑色墨水，特別是適合用於噴水。【圖式簡單說明】無【主要元件符號說明】無 9089 201237111 As apparent from the results of Table 22, the inks of the respective examples were extremely excellent in ozone gas resistance as compared with the inks of Comparative Examples 1 to 6. In other words, it is apparent that the chromatic aberration (Δ E) after the ozone gas resistance test is extremely small, and the change/fading caused by the ozone gas is less. Further, it is apparent that the robustness is not lowered by the medium, and a high-quality recorded image can be obtained. [Industrial Applicability] Black ink for various ink recordings such as writing instruments The black ink composition of the present invention is suitable for black ink for recording, and is particularly suitable for water spray. [Simple description of the diagram] None [Key component symbol description] None 90

Claims

201237111 VII. Patent application scope: An ink composition comprising: a pigment (1) and a pigment (11), wherein the pigment (I) is at least one of the pigments represented by the following formula (1), and each other a pigment which is at least one kind of a dye represented by the following formula (2) or a salt thereof;

[In the formula (1), R represents: (C1 to C4) an alkyl group; a (C1 to C4) alkyl group which is substituted by a thiol group; a phenyl group substituted with a sulfo group; or a carboxyl group, and R2 represents: a cyano group; an amine carbenyl group; or a carboxyl group, R and R each independently represent: a hydrogen atom; (C 1 to C 4) alkyl group; a halogen atom; (C1 to C4) alkoxy group; or a sulfo group, and R represents: (C1 to C4) alkylthio group; or (C1 to C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxyl group, a sulfo group and a carboxyl group, and R6 represents a (C1 to C4) alkane a carbonylamino group, R7 represents: a (C1 to C4) alkylthio group; or a (C1 to C4) alkyl sulfide substituted with at least one selected from the group consisting of a hydroxyl group, a sulfo group and a carboxymethyl group. a group, R represents a (C1 to C4) alkylcarbonylamino group, and R9 and R1Q each independently represent a hydrogen atom; a carboxyl group; a sulfo group; B 91 201237111 a mercaptoamine group; a chlorine atom; (Cl~C4) alkyl group; (Cl~C4) alkoxy group; or substituted by at least one group selected from the group consisting of a base group, a (c 1 to C4) alkoxy group, an exact group and a slow group (C1 to C4) Alkoxy, R1 1 to R·13 are each independently represented by a hydrogen atom; a stilbene; a hydroxy group; an ethionyl group; a chlorine atom; a cyano group; a nitro group; an amine sulfonyl group; and a (C1 to C4) alkyl group; (C1 to C4) alkoxy group; (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxyl group, a (ci~C4) alkoxy group, a sulfo group and a carboxyl group; (C1 to C4) alkanesulfonyl; or (C1 to C4) alkanesulfonyl substituted by at least one selected from the group consisting of a hydroxyl group, a sulfo group and a carboxyl group;

Η Η [In the formula (2), hydrazine and hydrazine are independently represented by a phenyl group; a naphthyl group; or a group having one azo bond; the groups may be derived from a thiol group, a hydrazine group, a thiol group, and C4) at least one selected from the group consisting of an alkylamino group is substituted]. [2] The ink composition according to Item 1, wherein 'in the above formula (1), R1 is a methyl group or a phenyl group, R is a cyano group or an amine methyl group, and r3 is a hydrogen atom; Or a methoxy group, R4 is a sulfo group, R is a (C1~C4)alkylthio group substituted by a sulfo group or a carboxyl group, 92 201237111 R6 is a (Cl~C4) alkylcarbonylamino group, and R7 is a sulfonate. (C1~C4)alkylthio group substituted by a base or a carboxyl group, R8 is a (C1~C4) alkylcarbonylamino group, R9 is a repeating group (C1~C4) alkoxy group, and R is a (C1~C4) alkyl group. Or an acetamidoamine group, R11 to R13 are each independently: a hydrogen atom; a carboxyl group; a sulfo group; a gas atom, an exact group, a methyl group; a decyloxy group; an amine group; or a performance base or a slow base. Substituting (C1~C4) alkanesulfonyl. The ink composition according to claim 1, wherein, in the above formula (2), A and B are each independently: having at least one selected from the group consisting of a sulfo group and a carboxyl group; A substituent and having a group of azo bonds. 4. The ink composition according to claim 1, wherein at least one of the pigment (III) and the pigment (IV) is further contained, and the pigment (ΙΠ) is represented by the following formula (3) a pigment or a salt thereof, the pigment (IV) being a water-soluble yellow dye which is not contained in the above formula (1) to (ΠΙ) and has 1 to 2 azo groups in one molecule: HO3S S03H ^-N=nh([}-N=

(3) so3h [In the formula (3), 113 represents: a hydrogen atom; a hydroxyl group; a carboxyl group; an unsubstituted (C1 to C4) alkyl group; and is substituted by a radical or a (C1 to C4) alkoxy group (C1 to C4) An alkyl group; an unsubstituted (C1 to C4) alkoxy group; (C1 93 201237111 to C4) alkoxy group substituted by a hydroxyl group or a (C1 to C4) alkoxy group; an unsubstituted (cl~c4) alkylamine (C1~C4)alkylamino group substituted by hydroxy or (Cl~C4) alkoxy; carboxy(C1~C5)alkylamino group; bis(carboxy(C1~C5)alkyl)amino group Unsubstituted (C1~C4) alkanoylamino group; (C1~C4) alkanoylamino group substituted by hydroxy or (C1~C4) alkoxy group; unsubstituted phenylamino group; benzene ring a phenylamine group substituted with at least one selected from the group consisting of a carboxyl group, a sulfo group, and an amine group; a sulfo group; a halogen atom; or a urea group, and X represents an aliphatic amine substituted with a carboxyl group or a sulfo group. base]. 5. The ink composition according to claim 4, wherein the pigment represented by the above formula (3) is represented by the following formula (4):

[In the formula (4), X represents a mono(C1-C5)alkylamino group having a carboxyl group or a sulfo group, or a di(C1-C5)alkylamino group having a carboxyl group or a sulfo group]. 6. The ink composition according to claim 4, which comprises both the dye (III) and the dye (IV). The ink composition according to the first aspect of the invention, wherein the ratio of the dye (1) is 50 to 90% by mass, the coloring matter (in the total mass of the dye contained in the chemical composition) The ratio of Π) is 1 to 10% by mass. 8. The ink composition according to claim 1, wherein the phase is 20% by mass. The total mass of the ink X composition is 'the total amount of the above-mentioned pigment (I) and the aforementioned pigment (η) is 0.1 94 201237111. 9. The ink composition according to claim 6, wherein the ink composition In the total mass of the dye contained in the dye, the ratio of the dye (I) is 50 to 90% by mass. The ratio of the dye (η) is 1 to 1% by mass, and the ratio of the dye (III) is 5 to 2%. The mass %, the ratio of the above dye (IV) is 4 to 20% by mass. The ink composition according to Item 6, wherein the pigment (?), the dye (H), the dye (III), and the pigment (Iv) are the total mass of the ink composition. The total content of )i 〜2 〇 mass% ^ 11. The ink composition as described in claim 1, which is used for inkjet recording. 12. An inkjet recording method using the ink composition according to any one of the items of the present invention, wherein the ink droplets of the ink are ejected according to a recording signal, and are Record materials for recording. 13. The inkjet recording method according to claim 12, wherein the recording material is a sheet for information transmission. 14. The ink jet recording method according to claim 13, wherein the information transfer sheet is a sheet having an ink receiving layer, and the ink receiving layer contains a porous white inorganic material. 15. A coloring body which is colored by the ink composition according to any one of the above claims. 16. An ink jet printer loaded with a container comprising the K composition of any one of the claims to the third item. 95 201237111 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: