TW201005048A

TW201005048A - Ink composition, inkjet recording method and colored body

Info

Publication number: TW201005048A
Application number: TW98114421A
Authority: TW
Inventors: Yoshiaki Kawaida; Takashi Yoshimoto; Takahiko Matsui
Original assignee: Nippon Kayaku Kk
Priority date: 2008-05-07
Filing date: 2009-04-30
Publication date: 2010-02-01
Also published as: JPWO2009136577A1; WO2009136577A1

Abstract

Provided is pigment for black ink and ink compositions thereof that are highly soluble in media having water as the main component, that are stable even when high concentration aqueous solutions are stored for long periods, that have high density in printed images, that do not produce bronzing in images wherein high concentration solutions have been printed, that have favorable color rendering, and that provide black recorded images, said images having excellent fastness. As the pigment for black ink, pigment (I) represented by formula (1) or salts thereof, and pigment (II) represented by formula (2) or a tautomer thereof, or salts thereof, are used. [In formula (1), Ra represents a C1-C4 alkyl group and X represents a sulfo-substituted aliphatic amino group.] [In formula (2), R1 represents a C1-C4 alkyl group, R2 represents a cyano group, R3 and R4 each independently represents a hydrogen atom or a sulfo group, the rings wherein R5 to R7 or R8 to R10 are substituted represent benzene rings when rings represented by dotted lines are absent and naphthalene rings when said rings are present, R5 to R7 each independently represents a hydrogen atom, a C1-C4 alkyl group, or a sulfo-substituted C1-C4 alkoxy group, R8 to R10 each independently represents a hydrogen atom, a C1-C4 alkyl group, or a sulfo-substituted C1-C4 alkylthio groups, and Group A represents a sulfo-substituted 2-naphthothiazolyl group.]

Description

201005048 六、發明說明：【發明所屬之技術領域】本發明係有關於一種至少含有2種色素之墨水組成物、使用該墨水組成物之喷墨記錄方法、及藉由該墨水組成物而著色之著色體。【先前技術】各種顏色記錄方法中的代表性方法之一亦即利用嘴墨印表機之記錄方法，係產生墨水的小滴，使其附著於各種被記錄材料（紙、膜、布$等）上來進行記錄。該方法由於記錄頭與被記錄材料並不直接接觸，故產生的聲音少而安靜，並且由於具有容易小型化、高速化之優點二近年來該方法迅速普及，今後亦可望有較大增長。於先前’鋼筆、氈筆(felt pen)等用之墨水以及喷墨記錄用之墨水係使用將水溶性色素溶解於水性介質中而形成之水性墨水。另外，㈣等水性墨水中，A 了防止墨水堵塞在筆尖或喷墨喷嘴中，-般添加有水溶性有機溶劑。並且對於該等墨水，業界要求：提供濃度充分之記錄圖像， :產：筆尖或喷嘴之堵塞，在被記錄材料上之乾燥性良，、墨彡’並且保存穩定性優異、印刷圖像上不易發生別^澤性^卜，對於所使用之水溶性色素，業界特性：：：在水中的溶解度高’並且在墨”所添加之水溶有機溶劑中之溶解度高。進而，業界對所形成之圖像， 201005048 要求具有耐水性、耐光性、* 像堅牢性。以化性氣㈣、耐濕性等圖所謂金屬光澤性，係和 ^ m m 热 ' 色素的融合或墨水的吸收不良等原因，以致色素在光个 B ’式的表面呈金屬片狀、具有金屬般的光澤而閃亮的金屬& 、之發生的容易性。若發:=(又稱金光浮色現象) 質、印刷濃度之各方面，==現象，則光澤、印刷品所謂耐氧化性氣體性，“ Μ通常又稱為耐氣體性，其係指對如下現象之耐受性：存处氧^ ;二氣中而具有氧化作用之臭氧氣體等，在s己錄紙中與色或褪色。具有此種作用…：’使所印刷之圖像變色 NOx、SOx等，但是” 、軋氣體氣體係進一步促進喷墨纪二等氧化性氣艘中’臭氧物f，4α & 〇、圖像之變色或褪色現象的原因 # ^ 14礼體性之程度的加速試驗， φ 、' 該由氧化性氣體所引起之變色戋褪色現象係噴墨圖像之特徵，因/ 要ίή锶η 町果氧氣體性之提高成為最重 #^^陕墨水之乾燥，並且減少高晝質時之滲墨，設置於相片 ^ a , ^ ^ 質噴墨專用紙之表面的墨水吸收層大多使用由白色盔應此之所得之乡隸材料，於如 [ <疋録紙上明顯看到，# 臭氡乳體所引起的變色或褪色。又’所謂的耐濕性，係 ^ Λ ’、a對如下現象之耐受性：將所耆色之被記錄材料保存於 t ^ ^ 熬度的虱氮下時，被記錄材料中之色素滲出的現象。若 a m ^ 巴京之滲出，則由於在特別謀永相片風格般的高精細畫 —賢之圖像中’圖像品質會顯著降 4 201005048 耐濕求的低，所以盡量使這樣的滲墨減少是很重要的。因此，性亦與前述的耐臭氧氣體性同樣是喷墨用重要課題。 ' 今後’業界為了擴大使用墨水之印刷方法的使用領域’而對喷墨記錄所使用之墨水組成物以及由其著色色趙，強烈要求進—井招+以進步“耐水性、耐光性、耐濕性、耐臭氧氣體性。胃[Technical Field] The present invention relates to an ink composition containing at least two kinds of pigments, an inkjet recording method using the ink composition, and coloring by the ink composition Coloring body. [Prior Art] One of the representative methods of various color recording methods, that is, the recording method using the ink jet printer, is to produce droplets of ink to be attached to various recorded materials (paper, film, cloth, etc.) ) Come up for recording. In this method, since the recording head is not in direct contact with the material to be recorded, the generated sound is quiet and small, and the method is easy to miniaturize and speed up. In recent years, the method has been rapidly spread, and it is expected to have a large increase in the future. In the ink used for the 'pen pen, felt pen, etc., and the ink for inkjet recording, an aqueous ink formed by dissolving a water-soluble pigment in an aqueous medium is used. Further, in (4) aqueous inks, A prevents the ink from being clogged in the nib or the ink jet nozzle, and a water-soluble organic solvent is generally added. And for these inks, the industry requires: to provide a sufficient concentration of recorded images, production: clogging of the tip or nozzle, good drying on the material to be recorded, ink 彡 'and excellent storage stability, printed image It is not easy to occur. For the water-soluble pigments used, the industry characteristics are as follows:: the solubility in water is high 'and the solubility in the water-soluble organic solvent added to the ink is high. Further, the industry has formed Image, 201005048 Requires water resistance, light resistance, * image fastness. The so-called metallic luster of chemical gas (4), moisture resistance, etc., and the fusion of ^ mm heat' pigment or poor absorption of ink, etc. Therefore, the coloring of the pigment on the surface of the light B' type is metal sheet-like, metallic-like luster, and the easiness of the metal & shiny: = (also known as golden floating phenomenon) quality, printing density In all aspects, == phenomenon, gloss, print, so-called oxidation-resistant gas, "Μ is often referred to as gas resistance, which refers to the tolerance to the following phenomena: the presence of oxygen ^; The effect of the ozone gas, etc., in the s-hexyl and the color recording paper or discoloration. Has such a role...: 'Make the printed image discolored NOx, SOx, etc., but", the gas gas system further promotes the iodine f, 4α & 〇, image Causes of discoloration or fading phenomenon # ^ 14 Accelerated test of the degree of rituality, φ, 'The discoloration caused by oxidizing gas 戋 fading phenomenon is characteristic of inkjet image, due to / ή锶町町The improvement of the oxygen gas property becomes the heaviest of the drying of the ink, and the ink bleed when the high enamel is reduced, and the ink absorbing layer provided on the surface of the photo inkjet paper is mostly used by the white helmet. The material of the township that should be obtained by this is clearly seen on [ < 疋纸纸 , , # # # # 变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色变色Tolerance: The phenomenon of pigment bleed out in the recorded material when the recorded material of the ochre is stored under the 虱虱 t 。。。。。。。。。 am am am am am am am am am am am am Photo-style high-definition painting - image quality in the image of Yin Significantly lower 4 201005048 It is very low in resistance to moisture, so it is important to reduce such bleed as much as possible. Therefore, the same as the above-mentioned ozone-resistant gas, it is an important issue for inkjet. The field of use of the printing method's ink composition used for inkjet recording and its coloring color are strongly required to advance into the well-being to improve "water resistance, light resistance, moisture resistance, ozone gas resistance." stomach

各種色調之墨水係由各種色素來製備，該等令黑色墨水不僅詩列印文字資訊之用途，也是用於全彩圖像中之重要墨水。但是農色區域與淡色區域均為中性色調，且列印滚度高，冑而，色調之光源依賴性小而呈良好黑色，在此種色素的開發上有著許多技術上的困難點，雖然進行著龐大的研究開發，但具有充分性能者仍然很少。所以，一般是混合多種各式色素而製備黑色墨水。但是若混合多種色素來製備墨水，則相較於以單一色素來製備墨水的情形會有下述等問題：1)色調會依介質（被記錄材料）而不同；2)變色會由於光或臭氧氣體所致之色素的分解而特別劇烈。作為印刷物之各種耐久性良好的喷墨用黑色墨水組成物’例如提出有專利文獻1等。此墨水組成物，以黑色而言其色調非常良好’對於印刷物之圖像堅牢性也是有著大幅改良的墨水組成物，但是仍期望特別對於耐臭氧氣體性進一步改善，而仍無法提供充分滿足市場要求的製品。 [專利文獻1]國際公開第2007/077931號小冊子 5 201005048 [專利文獻2]國際公開第2〇〇6/〇〇1274號小冊子【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 . 在長時間保存時也很安定，濃色及淡色印刷時均能呈現無 . 色調而中性的黑色至灰色’所列印圖像的濃度非常高，各、•介質的色調也無變化’可賦予黑色的記錄圖像，印刷後的各種圖像保存性亦即耐水性、耐光性、耐氧化性氣體性、对漁II等’且特別是耐臭氧氣體性及耐光性均非常優異。 L解決問題之技術手段]The inks of various shades are prepared from various pigments, which make the black ink not only useful for printing text information, but also for important inks in full-color images. However, the agro-color area and the light-colored area are both neutral tones, and the printing gradation is high, and the light source dependence of the color tone is small and good black. There are many technical difficulties in the development of such pigments, although There is a huge amount of research and development, but there are still few people with sufficient performance. Therefore, it is common to mix a plurality of various dyes to prepare a black ink. However, if a plurality of pigments are mixed to prepare an ink, there are the following problems as compared with the case of preparing a single pigment: 1) the hue varies depending on the medium (recorded material); 2) the discoloration may be due to light or ozone The decomposition of the pigment by gas is particularly severe. For example, Patent Document 1 and the like are proposed as various black ink compositions for inkjet which are excellent in durability. This ink composition has a very good hue in black'. It is also a greatly improved ink composition for image fastness of printed matter, but it is still expected to further improve ozone gas resistance, and still cannot fully satisfy market requirements. Products. [Patent Document 1] International Publication No. 2007/077931 Booklet 5 201005048 [Patent Document 2] International Publication No. 2/6/1274 [Invention Summary] [Problems to be Solved by the Invention] The object of the present invention is Provides a water-based black ink composition, which is also stable when stored for a long time, and can be rendered in both rich and light-colored printing. The color tone and neutral black to gray 'the density of the printed images are very high, each • The color of the medium does not change. It can give a black recorded image. The various images after printing are also water-resistant, light-resistant, oxidizing-resistant, gas-resistant, and especially ozone-resistant. Both sex and light resistance are excellent. L technical means to solve the problem]

本發明者們為了解決tM 、述問題而反覆精心研究，結果發現含有特定之至少2種色素 M翻，w &京的墨水組成物，可解決上述The present inventors have intensively studied in order to solve the problem of tM and the above-mentioned problems, and as a result, it has been found that the ink composition containing at least two kinds of pigments, w &

問題，從而完成本發明。 IThe problem is thus completed by the present invention. I

亦即’本發明係關於： 1) 由下述式（1)所示之色素所不之色素（II)或其互變 "'種墨水組成物，其含有： ⑴或其鹽；與由下述式（2) 異構物、或該等之鹽， [化學式1] 6 (1) 201005048That is, the present invention relates to: (1) a pigment (II) which is not a pigment represented by the following formula (1) or an interconverting ink composition thereof, which comprises: (1) or a salt thereof; Isomer of the following formula (2), or a salt thereof, [Chemical Formula 1] 6 (1) 201005048

(式（1)中，(in equation (1),

Ra表示氫原子；羥基；羧基；可經羥基或C1〜C4炫氧基取代之C1〜C4烷基；可經羥基或C1〜C4烷氧基取代之C1〜C4烷氧基；可經羥基或C1〜C4烷氧基取代之C1 〜C4烧基胺基；羧基C1〜C5烷基胺基；雙（羧基C1〜C5 烷基）胺基；可經羥基或C1〜C4烷氧基取代之C1〜C4烷酿基胺基；苯環可經羧基、磺基或胺基取代之笨基胺基；磺基；_原子；或是脲基， X表不具有羧基或磺基之脂肪族胺基）， [化學式2]Ra represents a hydrogen atom; a hydroxyl group; a carboxyl group; a C1 to C4 alkyl group which may be substituted by a hydroxyl group or a C1 to C4 decyloxy group; a C1 to C4 alkoxy group which may be substituted by a hydroxyl group or a C1 to C4 alkoxy group; C1 to C4 alkoxy substituted C1 to C4 alkylamino group; carboxy C1 to C5 alkylamino group; bis(carboxy C1 to C5 alkyl)amino group; C1 which may be substituted by a hydroxyl group or a C1 to C4 alkoxy group a C4 alkylamino group; a phenyl ring which may be substituted with a carboxyl group, a sulfo group or an amine group; a sulfo group; an atom; or a urea group; X represents an aliphatic amine group having a carboxyl group or a sulfo group. ), [Chemical Formula 2]

kC 2)中 R表不羧基、未經取代或經羧基取代之C1〜C4烧或者未經取代或經磺基取代之苯基， ^為氰基、胺甲ϋ基、或叛基，及R刀別獨立為氫原子、氣原子、續基、未經] C4烷基、或未經取代之C1〜C4烷氧基， 201005048 R至R所取代之環，於虛線所示之環並不存在時為苯環，於虛線所示之環存在時為萘環，KC 2) a phenyl group in which R is not carboxyl group, unsubstituted or substituted by a carboxyl group, or unsubstituted or substituted by a sulfo group, ^ is a cyano group, an aminomethyl group, or a thiol group, and R The cleavage is independently a hydrogen atom, a gas atom, a contiguous group, an unsubstituted C4 alkyl group, or an unsubstituted C1~C4 alkoxy group. The ring substituted by R10 to R is not present in the ring shown by the dotted line. The benzene ring is a naphthalene ring in the presence of a ring indicated by a broken line.

R5至V分別獨立表示氫原子；氯原子；續基；羧基；胺磺醯基；胺甲醯基；未經取代之ci〜c4烷基；未經取代，或者經羥基、未經取代之C1〜c4烷氧基:羥基CM〜C4烷氧基、磺基、或羧基取代之幻〜以烷氧基；未經取代，或者經羥基、磺基、或羧基取代之單或二〇〜 C4烷基胺基；未經取代，或者經羥基或羧基取代之 C4烷基羰基胺基；未經取代，或者經羥基、磺基、或鲮基取代之N’_C1〜C4烷基脲基；未經取代，或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基、或羧基取代之苯基胺基；未經取代，或者苯環經氣原子、未經取代之 C1〜C4烷基、硝基、磺基 '或羧基取代之苯甲醮基胺基；或者未經取代，或者笨環經氣原子、未經取代之C1〜c4 烧基、硝基、磺基、或羧基取代之苯基磺醯基胺基， R8至R1G所取代之環，於虛線所示之環並不存在時為苯環，於虛線所示之環存在時為萘環， R至R分別獨立表示氫原子；氣原子；經基；續基；羧基；胺磺醯基；胺甲醯基；未經取代之C1〜C4烧基；未經取代’或者經羥基、未經取代之C1〜C4烷氧基、經基C1〜C4烧氧基、續基、或缓基取代之C1〜C4燒氧基· 經羥基、磺基、或羧基取代之C1〜C4烷硫基；未經取代，或者經羥基、磺基、或羧基取代之單或二C1〜C4院基胺基；未經取代’或者經羥基或羧基取代之C1〜C4烧基幾 201005048 ‘基胺基；未經取代，或者經羥基、磺基、或羧基取代之N,_cl 〜C4烷基脲基；未經取代，或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基、或羧基取代之苯基胺基；未經取代，或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基、或羧基取代之苯甲醯基胺基；或者未經取代， • 或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基、或羧基取代之苯基磺醯基胺基， # 基A係未經取代或具有取代基之2-萘并噻唑基，於該 2-萘并噻唑基具有取代基之情形時，可具有選自由：氣原子；磺基；硝基；羥基；胺磺醯基；未經取代之c丨〜C4 烷基；未經取代’或者經羥基、C1〜C4烷氧基、磺基、或羧基取代之C1〜C4烷氧基；未經取代，或者經羥基、磺基、或羧基取代之C1〜C4烷基磺醯基；以及未經取代，或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基或幾·基取代之苯基績醯基所組成之群組中的取代基 • 2) 如上述1)所述之墨水組成物’其中在墨水組成物中所含有之全部色素是下述兩者：由式（1)所示之色素（I) 或其鹽’與由式（2)所示之色素（Π)或其互變異構物、或該等之鹽。 3) 如上述1)或2)所述之墨水組成物’其中上述色素（I) 是由下述式（3)所示之色素， [化學式3] 9 201005048R5 to V each independently represent a hydrogen atom; a chlorine atom; a contiguous group; a carboxyl group; an amine sulfonyl group; an amine carbaryl group; an unsubstituted ci~c4 alkyl group; an unsubstituted or a hydroxy group, an unsubstituted C1 group ~c4 alkoxy: hydroxy CM~C4 alkoxy, sulfo, or carboxy substituted phantom ~ alkoxy; unsubstituted, or substituted by hydroxy, sulfo, or carboxyl group, mono or di- to C4 alkane Alkylamino; unsubstituted, or C4 alkylcarbonylamino group substituted by hydroxy or carboxy; unsubstituted, or N'_C1 to C4 alkylureido substituted by hydroxy, sulfo, or thiol; Substituted, or a phenylamine group in which a benzene ring is substituted with a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group, or a carboxyl group; an unsubstituted or a benzene ring via a gas atom, an unsubstituted C1 group ～C4 alkyl, nitro, sulfo' or carboxy substituted benzhydrylamino; or unsubstituted, or a stupid ring through a gas atom, unsubstituted C1~c4 alkyl, nitro, sulfo, Or a carboxy-substituted phenylsulfonylamino group, a ring substituted by R8 to R1G, which is a benzene ring when the ring shown by the dotted line is not present, The ring shown by the line is a naphthalene ring, and R to R each independently represent a hydrogen atom; a gas atom; a meridine; a contig; a carboxyl group; an amine sulfonyl group; an amine carbenyl group; an unsubstituted C1 to C4 alkyl group. Unsubstituted 'or C1~C4 alkoxy group via a hydroxyl group, an unsubstituted C1~C4 alkoxy group, a C1~C4 alkoxy group, a contiguous group or a slow group; a hydroxyl group, a sulfo group, Or a carboxy-substituted C1-C4 alkylthio group; unsubstituted, or a mono- or di-C1-C4-based amine group substituted by a hydroxy group, a sulfo group, or a carboxy group; unsubstituted or substituted by a hydroxyl group or a carboxyl group; C4 alkyl group 201005048 'Amino group; unsubstituted, or N,_cl~C4 alkylureido group substituted by hydroxy, sulfo, or carboxyl group; unsubstituted, or benzene ring by gas atom, unsubstituted C1-C4 alkyl, nitro, sulfo, or carboxy substituted phenylamine; unsubstituted, or phenyl ring via a gas atom, unsubstituted C1 to C4 alkyl, nitro, sulfo, or carboxyl Substituted benzhydrylamine; or unsubstituted, or phenyl ring via a gas atom, unsubstituted C1 to C4 alkyl, nitro, sulfo group Or a carboxy-substituted phenylsulfonylamino group, a 2-naphthylthiazolyl group having an unsubstituted or substituted group, wherein the 2-naphthylthiazolyl group may have a substituent selected from the group consisting of : a gas atom; a sulfo group; a nitro group; a hydroxyl group; an amine sulfonyl group; an unsubstituted c丨~C4 alkyl group; an unsubstituted 'either substituted by a hydroxyl group, a C1 to C4 alkoxy group, a sulfo group, or a carboxyl group a C1 to C4 alkoxy group; an unsubstituted or C1 to C4 alkylsulfonyl group substituted by a hydroxy group, a sulfo group or a carboxyl group; and an unsubstituted or phenyl ring via a gas atom, an unsubstituted C1 to C4 a substituent in the group consisting of an alkyl group, a nitro group, a sulfo group or a benzyl group substituted with a phenyl group; 2) an ink composition as described in 1) above, which is contained in the ink composition All the pigments are the following: a dye (I) represented by formula (1) or a salt thereof and a dye (Π) represented by formula (2) or a tautomer thereof, or a salt thereof . 3) The ink composition according to the above 1) or 2) wherein the dye (I) is a dye represented by the following formula (3), [Chemical Formula 3] 9 201005048

(式（3)中’X具有與式（！）相同之含義）。 4) 如上述1)至3)中任一項所述之墨水組成物，其中χ 是具有羧基或磺基之單Cl〜C5烷基胺基或二Cl〜C5烷基 5) 如上述1)至4)中任一項所述之墨水組成物，其中χ 是磺基乙胺基。 6) 如上述1)至5)中任一項所述之墨水組成物，其中上述色素（II)是由下述式（4)所示之色素， [化學式4](In the formula (3), 'X has the same meaning as the formula (!)). 4) The ink composition according to any one of the above 1), wherein χ is a mono-Cl~C5 alkylamino group having a carboxyl group or a sulfo group or a diCl~C5 alkyl group 5) as in the above 1) The ink composition according to any one of 4, wherein χ is a sulfoethylamino group. The ink composition according to any one of the above 1 to 5, wherein the pigment (II) is a dye represented by the following formula (4), [Chemical Formula 4]

(式（4)中，基A 'R1至R10，具有與式（2)相同之含義）。 7) 如上述1)至6)中任一項所述之墨水組成物’其中上 201005048 述色素（II)是由下述式（5)所示之色素， [化學式5](In the formula (4), the groups A 'R1 to R10 have the same meanings as in the formula (2)). 7) The ink composition according to any one of the above 1) to 6) wherein the pigment (II) is a dye represented by the following formula (5), [Chemical Formula 5]

基A、R至R4具有與式（1)相同之含義’The bases A, R to R4 have the same meaning as the formula (1)'

R5及R7分別獨立表示氫原子；氣原子；未經取代，或者經經基或竣基取代之Cl〜C4烷基羰基胺基；未經取代之C1〜C4烧基；或是，未經取代，或者經磺基或羥基取代之C1〜CM烷氧基，R6表示氫原子， R至r1g分別獨立表示氫原子；氣原子；未經取代’ 或者經經基或緩基取代之以〜以烷基羰基胺基；磺基C1 C4烷氧基；未經取代之c丨〜C4烷基；未經取代，或者經場基取代之C1〜C4燒氧基；或是，經續基或叛基取代之C1〜C4烷硫基；R9表示氫原子 8) 上述1)至7)中任一項所述之墨水組成物’其中基 A是由下述式U)所示之基， [化學式6]R5 and R7 each independently represent a hydrogen atom; a gas atom; an unsubstituted or a C1-C4 alkylcarbonylamino group substituted by a thiol or a fluorenyl group; an unsubstituted C1 to C4 alkyl group; or, unsubstituted Or a C1~CM alkoxy group substituted by a sulfo group or a hydroxyl group, R6 represents a hydrogen atom, and R to r1g each independently represent a hydrogen atom; a gas atom; an unsubstituted ' or a group substituted with a base or a slow group Alkylcarbonylamino group; sulfo C1 C4 alkoxy group; unsubstituted c丨~C4 alkyl group; unsubstituted or C1-C4 alkoxy group substituted by a field group; or, a contiguous group or a thiol group The substituted C1 to C4 alkylthio group; R9 represents a hydrogen atom. The ink composition according to any one of the above 1) to 7) wherein the group A is a group represented by the following formula U), [Chemical Formula 6] ]

11 201005048 • (式（6)中， R11至R14分別獨立表示選自由：氫原子；氣原子；磺基’硝基，經基；胺確醢基；未經取代，或者經經基、未經取代之C1〜C4烷氧基、磺基、或羧基取代之ci〜C4烷氧基；以及未經取代，或者經羥基、磺基、或綾基取代之 C1〜C4烧基項酿基所組成之群組中之基）。 9) -0 如上述8)所述之墨水組成物，其中R〗為甲基，R2為氰基或胺曱醯基，R3為氫原子，R4為磺基，R5為磺基丙氧基或磺基丁氧基，R6為氫原子，R7為氫原子、氣原子、乙酿基胺基、甲基、乙基、曱氧基、乙氧基、磺基丙氧基或確基丁氧基’R為項基丙硫基或績基丁硫基，R9為氫原子， R10為氫原子、氣原子、乙醯基胺基、甲基、乙基、甲氧基、乙氧基或磺基丙氧基，至R〗4之中的三個為磺基、一個為氮原子。 • 10) 如上述1 )至9)中任一項所述之墨水組成物，其中在墨水組成物中所含有之色素（1)或其鹽、以及色素（ιι) 或其互變異構物、或該等之鹽的比率是10〜30質量％，鹽的總質量中，色素（1)或其色素（II)或其互變異構物、或該等之鹽的比率是70〜90質量〇/〇 11) 如上述1)至10)中任一袓對於墨水組成物之總質量，項所述之墨水組成物，其中在墨水組成物中所含有之色 12 201005048 素（I)或其鹽、以及色素（π)或其互變異構物、或該等之鹽的總質量是2〜8質量％。 12) 如上述1)至11)中任一項所述之墨水組成物，其係使用於噴墨記錄。 13)11 201005048 • (in the formula (6), R11 to R14 are each independently selected from: hydrogen atom; gas atom; sulfo group 'nitro group, thiol group; amine group; unsubstituted, or via base group, Substituted C1 to C4 alkoxy, sulfo, or carboxy substituted ci~C4 alkoxy; and unsubstituted, or substituted by a hydroxy, sulfo, or fluorenyl C1~C4 alkyl group The base in the group). 9) -0 The ink composition according to the above 8), wherein R is a methyl group, R 2 is a cyano group or an amine fluorenyl group, R 3 is a hydrogen atom, R 4 is a sulfo group, and R 5 is a sulfopropoxy group or Sulfobutoxy group, R6 is a hydrogen atom, and R7 is a hydrogen atom, a gas atom, an ethylamino group, a methyl group, an ethyl group, a decyloxy group, an ethoxy group, a sulfopropoxy group or a decyloxy group. 'R is a propylthio or a butylthio group, R9 is a hydrogen atom, and R10 is a hydrogen atom, a gas atom, an ethylamino group, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a sulfo group. The propoxy group, three of R R 4 are a sulfo group and one is a nitrogen atom. The ink composition according to any one of the above 1 to 9, wherein the pigment (1) or a salt thereof, and the pigment (Io) or a tautomer thereof thereof are contained in the ink composition, Or the ratio of the salt is 10 to 30% by mass, and the ratio of the pigment (1) or its pigment (II) or its tautomer, or the salt thereof is 70 to 90% by mass in the total mass of the salt. /〇11) The ink composition according to any one of the above 1) to 10) for the total mass of the ink composition, wherein the color contained in the ink composition is 12 201005048 (I) or a salt thereof And the total mass of the pigment (π) or its tautomer or the salt thereof is 2 to 8 mass%. 12) The ink composition according to any one of the above 1) to 11), which is used for inkjet recording. 13)

一種喷墨記錄方法’其中將如上述〇至12)中任一項所述之墨水組成物用作墨水，使該墨水的墨水滴按照記錄訊號而喷出，以在被記錄材料上進行記錄。 14) 如上述⑴所述之喷墨記錄方法，其中上述被記錄材料’係資訊傳遞用片材。 15) 其中上述資訊傳遞之墨水吸收層。如上述14)所述之喷墨記錄方法，用片材’具有一含有多孔性白色無機物 16) 一種著色體，其係藉由如上述υ 〜w王12)中杯一馆私述之墨水組成物而被著色。 17) Γ述16)所述之著色體’其著色係藉由喷墨印表機來進行 ⑷—種喷墨印表機’其裝填有含有如上述。至甲任—項所述之墨水組成物的容器。；主 13 12) 201005048 [功效] 本發明之墨水組成物，並無長時間保存後的結晶析出、物性變化、色調變化等，且儲藏穩定性良好。而且，本發明之墨水組成物可用於喷墨記錄、書寫用具，其記錄於喷墨專用紙時的記錄圖像的色調中性，即使作成濃度薄的墨水，也能獲得黑色的印刷物，且印刷濃度高，各種堅牢性亦即耐水性、耐光性、耐氧化性氣鱧性、耐濕性等，且特別是耐臭氧氣體性及耐光性均優異，色調之光源依賴性小。而且，#由與洋紅色、青色、黃色色素併用，而可進行耐光性及耐水性優異的全彩喷墨記錄。如此，本發明之墨水組成物，作為喷墨印刷用黑色墨水而極其有用。【實施方式】以下，對本發明加以詳細說明。另外，在本發明中，只要無特別說明，磺基、羧基等酸性官能基係以游離酸之參形式表示。又，「色素⑴或其鹽」及「色素（11)或其互，變異構物、或該等之鹽」，為了避免記載變得繁雜，故方便起見，分別簡略記載為「色素（1)」及「色素（11)」，而均包3 δ亥色素或其互變異構物、或者該等之鹽。本發明之墨水組成物，其特徵在於：至少含有由上述式（1)所示之色素（I)與由上述式（2)所示之色素（11) 的兩者。基於調色等目的，可含有此2種以外的色素，亦可不含有此2種以外的色素。換言之，本發明之墨水組成 14 201005048 物中所含有之全部色素，可以是由上述式⑴所示之色素 (I )及由上述式（2 )所示之色素（η )的兩者。本發明之墨水組成物所含有的色素（〗），是丨種以上之以式（1)表示的色素。亦即，色素（1)可以是由式（1) 所不之單一色素’也可以是由式（丨）所示之多種色素的混 . 合物’但實質上不含式（1)以外之色素。 - 在式（1)之色素中，Ra表示氫原子；羥基；羧基；可 φ 經羥基或C1〜C4烷氧基取代之Cl〜C4烷基；可經羥基或 C1〜C4烷氧基取代之C1〜C4烷氧基；可經羥基或C1〜 C4烷氧基取代之C1〜C4烷基胺基；羧基Cl〜c5烷基胺基’雙（叛基C1〜C5烧基）胺基；可經經基或ci〜C4烧氧基取代之C1〜C4烷醯基胺基；苯環可經羧基、磺基或胺基取代之苯基胺基；續基；齒原子；或是腺基。作為R ’可經經基或C1〜C4燒氧基取代之ci〜C4 烷基之具體例，可列舉：甲基、乙基、正丙基、異丙基、 ® 正丁基、異丁基、第二丁基、第三丁基等未經取代者；2- * ' ，經基乙基等經羥基取代者；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、第二丁氧基乙基、第三丁氧基乙基等經烷氧基取代者等。作為Ra’可經羥基或C1〜C4烷氧基取代之以〜以燒氧基之具體例，可列舉：曱氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基等未經取代者’ 2 -經基乙氧基、2 -經基丙氧基、3 -經基丙氧基.等經經基取代者；曱氧基乙氧基、乙氧基乙氧基、正丙氧基乙氡 15 201005048 基、異丙氧基乙氧基、正丁氧基乙氧基、曱氧基丙氧基、乙氧基丙氧基、正丙氧基丙氧基、異丙氧基丁氧基、正丙氧基丁氧基專經烧氧基取代者，2 -經基乙氧基乙氧基等經羥基及烷氧基複合取代者等。作為Ra’可經經基或C1〜C4烧氧基取代之C1〜C4 烷基胺基之具體例’可列舉：曱胺基、乙胺基、正丙胺基、異丙胺基、正丁胺基、異丁胺基等未經取代之單烷基胺基； N，N-二甲胺基、N，N-二乙胺基、n，N-二（正丙基）胺基、 N，N-二（異丙基）胺基等未經取代之二烷基胺基；羥基乙胺基、2-羥基丙胺基、3_羥基丙胺基等單（羥基取代烷基）胺基；雙（羥基乙基）胺基等雙（羥基取代烷基）胺基；甲氧基乙胺基、乙氧基乙胺基等單（烷氧基取代烷基）胺基；雙（甲氧基乙基）胺基、雙（2-乙氧基乙基）胺基等雙（烷氧基取代烷基）胺基等。 ‘ 作為Ra，羧基C1〜C5烷基胺基之具體例，可列舉：耱羧基甲胺基、羧基乙胺基、弟基丙胺基、羧基正丁胺基、 * 羧基正戊胺基等。作為Ra ’雙（羧基C1〜C5烷基）胺基之具體例，可列舉：雙（羧基甲基）胺基、雙（羧基乙基）胺基、雙（羧基丙基）胺基等。作為Ra，可經羥基或C1〜C4烷氧基取代之C1〜C4 院酿基胺基之具體例’可列舉：乙醯基胺基、正丙醯基胺基、異丙醯基胺基等未經取代者；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 201005048 胺基、3-羥基正丁醯基胺基等經羥基取代者；2_甲氧基正丙酿基胺基、3-曱氧基正丙醯基胺基、2-甲氧基正丁醯基胺基、3-甲氧基正丁醯基胺基等經烷氧基取代者等。作為Ra，苯環可經羧基、磺基或胺基取代之苯基胺基之具體例’可列舉：苯基胺基等未經取代者；羧基苯基胺基、雙羧基苯基胺基等經羧基取代者；磺基苯基胺基等經 ' 磺基取代者；胺基苯基胺基、二胺基苯基胺基等經胺基取 -φ 代者，二胺基磺基苯基胺基等分別經磺基及胺基取代者等。較佳的…是C1〜C4烷基，更佳為甲基。 X表示具有羧基或磺基之脂肪族胺基，可列舉：磺基 C1〜C5烷基胺基、羧基C1〜C5烷基胺基、二（磺基C1 〜C5烷基）胺基、二（羧基C1〜C5烷基）胺基等具有羧基或磺基之單C1〜C5烷基胺基或二（C1〜C5烷基）胺基。較佳的脂肪族之碳數是1或2 ^作為較佳的具體例，可列舉：磺基乙基胺基等磺基C1〜C5烷基胺基、二（羧基甲謇基）胺基等二（羧基C1〜C5烷基）胺基，其中又以磺基，乙基胺基等磺基C1〜C5烷基胺基更佳。式（丨）所示之色素（I)的最佳者’是由下述式（7)所示之色素。 [化學式7]An ink jet recording method wherein the ink composition according to any one of the above items is used as an ink, and ink droplets of the ink are ejected in accordance with a recording signal to perform recording on the material to be recorded. [14] The inkjet recording method according to (1) above, wherein the material to be recorded is a sheet for information transmission. 15) An ink absorbing layer in which the above information is transmitted. The inkjet recording method according to the above 14), wherein the sheet "haves a porous white inorganic substance 16" is a color body which is composed of an ink of a cup which is described in the above-mentioned υ~w王12) The object is colored. 17) The color body described in the above section 16) is colored by an ink jet printer (4) - an ink jet printer which is loaded with the contents as described above. A container for the ink composition of the above-mentioned item. Main 13 12) 201005048 [Efficacy] The ink composition of the present invention does not have crystal precipitation, physical property change, color tone change, etc. after long-term storage, and has good storage stability. Further, the ink composition of the present invention can be used for ink jet recording and writing instruments, and the hue neutrality of a recorded image when it is recorded on an ink jet special paper can obtain a black printed matter even if it is made into a thin ink. The concentration is high, and various fastnesses, that is, water resistance, light resistance, oxidation resistance, moisture resistance, moisture resistance, etc., are particularly excellent in ozone gas resistance and light resistance, and light source dependence of color tone is small. Further, # is used in combination with magenta, cyan, and yellow pigments to provide full-color inkjet recording excellent in light resistance and water resistance. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet printing. [Embodiment] Hereinafter, the present invention will be described in detail. Further, in the present invention, an acidic functional group such as a sulfo group or a carboxyl group is represented by a free acid parameter unless otherwise specified. In addition, "pigment (1) or its salt" and "pigment (11) or their mutual, isomers, or such salts" are simply described as "pigment (1) in order to avoid cumbersome description. And "pigment (11)", and all contain 3 δ hai pigment or its tautomers, or such salts. The ink composition of the present invention contains at least both of the dye (I) represented by the above formula (1) and the dye (11) represented by the above formula (2). The dyes other than the above two types may be contained for the purpose of toning or the like, and the dyes other than the above may not be contained. In other words, all of the dyes contained in the ink composition 14 201005048 of the present invention may be both the dye (I) represented by the above formula (1) and the dye (η) represented by the above formula (2). The pigment (?) contained in the ink composition of the present invention is a dye represented by the formula (1). That is, the dye (1) may be a single pigment of the formula (1) or a mixture of a plurality of pigments represented by the formula (丨), but substantially does not contain the formula (1). pigment. - In the dye of the formula (1), Ra represents a hydrogen atom; a hydroxyl group; a carboxyl group; a Cl~C4 alkyl group which may be substituted by a hydroxyl group or a C1 to C4 alkoxy group; may be substituted by a hydroxyl group or a C1 to C4 alkoxy group. a C1 to C4 alkoxy group; a C1 to C4 alkylamino group which may be substituted by a hydroxyl group or a C1 to C4 alkoxy group; a carboxyl group of a carboxyl group of a C1 to C5 alkyl group; a bis (derivative C1 to C5 alkyl) group; a C1 to C4 alkanoylamino group substituted by a phenyl group or a ci~C4 alkoxy group; a phenylamine group which may be substituted by a carboxyl group, a sulfo group or an amine group; a hydrazine group; a tooth atom; or a gland group. Specific examples of the ci~C4 alkyl group in which R ' may be substituted by a thiol group or a C1 to C4 alkoxy group include methyl group, ethyl group, n-propyl group, isopropyl group, butyl n-butyl group, and isobutyl group. Unsubstituted, second butyl, tert-butyl, etc.; 2-* ', substituted by hydroxy group such as benzyl group; methoxyethyl, ethoxyethyl, n-propoxyethyl, The isopropoxyethyl 'n-butoxyethyl group, the second butoxyethyl group, the third butoxyethyl group and the like are substituted by an alkoxy group. Specific examples of the alkoxy group in which Ra' may be substituted by a hydroxyl group or a C1 to C4 alkoxy group include a decyloxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. a second butoxy group, a third butoxy group or the like which is unsubstituted, such as a 2-ethoxymethyloxy group, a 2-phenylpropoxy group, a 3-propyloxy group, etc.; Oxyethoxyethoxy, ethoxyethoxy, n-propoxyacetam 15 201005048, isopropoxyethoxy, n-butoxyethoxy, decyloxypropoxy, ethoxypropyl Oxyl, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy, substituted by an alkoxy group, 2-hydroxy-ethoxyethoxy, etc. via a hydroxyl group and an alkoxy group Base compound replacement, etc. Specific examples of the C1 to C4 alkylamine group in which Ra' may be substituted by a trans group or a C1 to C4 alkoxy group may be exemplified by amidino group, ethylamino group, n-propylamino group, isopropylamine group, and n-butylamino group. Unsubstituted monoalkylamine group such as isobutylamino; N,N-dimethylamino, N,N-diethylamino, n,N-di(n-propyl)amine, N,N - an unsubstituted dialkylamino group such as bis(isopropyl)amine; a mono(hydroxy substituted alkyl)amino group such as hydroxyethylamino group, 2-hydroxypropylamino group or 3-hydroxypropylamino group; bis(hydroxyl group) a bis(hydroxy-substituted alkyl)amino group such as an ethyl)amino group; a mono(alkoxy-substituted alkyl)amino group such as a methoxyethylamino group or an ethoxyethylamino group; a bis(methoxyethyl) group; A bis(alkoxy-substituted alkyl)amino group such as an amine group or a bis(2-ethoxyethyl)amino group. Specific examples of Ra, a carboxyl group C1 to C5 alkylamine group include a carboxymethylamino group, a carboxyethylamino group, a dipropylamino group, a carboxyl-n-butylamino group, a *carboxy-n-pentylamino group, and the like. Specific examples of the Ra' bis(carboxy C1 to C5 alkyl)amino group include a bis(carboxymethyl)amino group, a bis(carboxyethyl)amino group, and a bis(carboxypropyl)amino group. Specific examples of the C1 to C4 arylamino group which may be substituted by a hydroxyl group or a C1 to C4 alkoxy group as Ra include an ethyl hydrazino group, a n-propyl decylamino group, an isopropenylamino group, and the like. Unsubstituted; hydroxyethylamino group, 2-hydroxy-n-propylamino group, 3-hydroxy-n-propylamino group, 2-hydroxy-n-butyl fluorenyl group 201005048 amine group, 3-hydroxy-n-decylamino group Hydroxy-substituted; 2-methoxy-n-propylaminomethyl, 3-decyloxy-n-decylamino, 2-methoxy-n-decylamino, 3-methoxy-n-decylamino, etc. Oxygen substituents, etc. Specific examples of the phenylamine group in which the benzene ring may be substituted with a carboxyl group, a sulfo group or an amine group include unsubstituted ones such as a phenylamino group; a carboxyphenylamino group, a biscarboxyphenylamino group, and the like. Substituted by a carboxyl group; a sulfophenylamino group or the like; a 'sulfo group substituted; an aminophenylamino group, a diaminophenylamino group or the like obtained by an amine group - φ, a diamino sulfophenyl group The amine group or the like is substituted by a sulfo group and an amine group, respectively. Preferred is a C1 to C4 alkyl group, more preferably a methyl group. X represents an aliphatic amine group having a carboxyl group or a sulfo group, and examples thereof include a sulfo C1 to C5 alkylamino group, a carboxyl group C1 to C5 alkylamino group, a di(sulfo C1 to C5 alkyl)amino group, and two ( A mono C1 to C5 alkylamino group or a di(C1-C5 alkyl)amino group having a carboxyl group or a sulfo group, such as a carboxyl group (C1 to C5 alkyl group). The preferred aliphatic carbon number is 1 or 2^. Preferred examples thereof include a sulfo C1 to C5 alkylamino group such as a sulfoethylamino group, and a di(carboxymethyl)amino group. The bis(carboxyl C1 to C5 alkyl)amino group is further preferably a sulfo C1 to C5 alkylamino group such as a sulfo group or an ethylamino group. The best one of the colorants (I) represented by the formula (?) is a dye represented by the following formula (7). [Chemical Formula 7]

⑺ 在本發明使用的色素（Π)，是i種以上之由式（2) 17 201005048 所示之色素。亦即，含 N θ , &各^ ^ 色素（11)可以疋由式（2)所示之單一色素，也可以是i 办十疋由式（2 )所示之多種色杳沾，5人从實質上不含式(2)以々k & 、U外之色素。上述式（2)所； ... 所不之三偶氮化合物，具有鐵里、有互變異構物，么七^ ( 了由式（2)所不之化合物以外，一般認為有下述式（8)、〔〇、 . . ^ )所示之化〇物等。該等亦包含於本發明由 ^(7) The dye (Π) used in the present invention is a dye represented by the formula (2) 17 201005048. That is, the N θ , & ^ ^ pigment (11) can be a single pigment represented by the formula (2), or can be a plurality of color sputum shown by the formula (2), 5 The person does not substantially contain the formula (2) with 々k & The tris-azo compound of the above formula (2) has iron and has a tautomer, and is a compound of the formula (2), and is generally considered to have the following formula. (8), 〇, ., . . . These are also included in the present invention by ^

包3發月中。再者，下述式（8)、（9)中，基A 環，包括由虚線所不之環在内，均具有與上述式（2)中相同之含義。 0具有 [化學式8]Pack 3 in the middle of the month. Further, in the following formulae (8) and (9), the base A ring, including the ring not shown by the broken line, has the same meaning as in the above formula (2). 0 has [Chemical Formula 8]

⑻ R1至R10所取代之環—“私(8) Ring replaced by R1 to R10 - "Private

(9) 於上述式⑺中，以示羧基、未經取代或⑽基取代之C1〜C4戈基、或者未經取代或經衫取代之苯基。於式⑺中的RU未經取代之C1〜C4统基的情形時，該炫基可為直鍵、支財之任—種，較佳為直鍵。作為未經取代之C1〜C4烷基之具體例，例如可列舉··甲其、 201005048 乙基、正丙基、正丁基等直鏈；異丙基、異丁基、第二丁基、第三丁基等支鏈。於該C1〜C4烷基具有羧基之情形時，該烷基部分包括較佳者在内，與上述相同即可。於R1為經羧基取代之C1〜C4烷基之情形時，作為較佳的具體例，可列舉羧基甲基、1羧基乙基、3羧基丙基等。作為式（2)中的Ri為未經取代、或經磺基取代之苯基時的具體例，例如可列舉··未經取代之苯基；或者2磺基苯基、4-磺基苯基、2,4_二磺基笨基、3,5_二磺基苯基等經續基取代之苯基等，其中確基通常為1 i 4個，較佳為 1至3個，更佳為1至2個。一上述式（2)中的Ri，在上述之中較佳為未經取代之 C1〜C4院基’或更佳為未經取代之苯基特佳為未經取代之C1〜C4烷基。作為於式（2)中的Ri的具體例，較佳為甲基、乙基、正丙基、第三丁基、苯基，更佳為甲基、正丙基、笨基，進而較佳為曱基、正丙基。 2上述式（2)中’ R2表示氰基、胺甲醯基、或缓基。作為R則任—者均佳，但較佳為氰基或胺甲酿基，更佳為氮基〇 2作為在式（2)中尺】與R2的組合，較佳為Rl為甲基為氰基、或Rl為甲基而R2為胺f醯基。更佳為前者 19 201005048 上述式⑺中，汉3及r4分别獨立表示氣原子、氣原子、確基、未經取代之C1〜C4燒基、或者未經取代之〇〜C4烷氧基。於式（2)中的R及R4為未經取代之a〜其之情形時，㈣基包括較佳者在内，與上述未經取狀 C1〜C4烷基之情形相同即可。於式（2)中的r及R4為未經取代之η〜a院氧基之情形時，該统氧基為直鍵或支鏈中之任一種均可。作為 =萁可列舉甲氧基、乙氧基、正丙氧基、異丙氧基：正丁氧基、第二丁氧基、第三丁氧基等。上述式（2)中的R3*R4，在上述之中更佳為氣原子、橫基、或未經取代之（^〜（^烷基。式⑺中的R3及C之具體例，較佳氣原子、續基、甲基、乙基、正丙基、異丙基、第三丁基，更佳為氫原子、磺基、甲基、異丙基，進而較佳為氫原子、磺基。式（2)中的R4R4,特佳為氧原子、甲基、另3外，R3與R4之組合較佳為R3為氫原子且r4為磺基、或 R3為磺基且R4為氫原子。較佳為前者的組合。、上述式⑴中’R5至RV斤取代之環於虛線所示之環並不存在時為苯環，於虛線所示之環存在時為萘環。其中較佳為虛線所示之環並不存在，亦即，、取代之環為苯環。較佳為…7所 A Vi R7分別獨立表示選自由下述所構成之群组之基：氣原子；氣原子；經基US緩基；胺續酿基；胺 20 201005048 甲醯基；未經取代之c 1〜C4烧基；未經取代，或者經羥基、未經取代之C1〜C4烷氧基、羥基C1〜C4烷氧基、磺基、或羧基取代之Ci〜C4烷氧基；未經取代，或者經羥基、磺基、或羧基取代之單或二C1〜C4烷基胺基；未經(9) In the above formula (7), a phenyl group which is represented by a carboxyl group, an unsubstituted or a substituted group (10), or a substituted or substituted phenyl group. In the case where the RU in the formula (7) is unsubstituted C1 to C4, the stimuli may be a direct bond or a rich one, preferably a straight bond. Specific examples of the unsubstituted C1 to C4 alkyl group include a straight chain such as methyl, n-propyl or n-butyl; acetal, isobutyl or t-butyl; Branches such as the third butyl group. In the case where the C1 to C4 alkyl group has a carboxyl group, the alkyl moiety may preferably be the same as described above. In the case where R1 is a C1-C4 alkyl group substituted by a carboxyl group, a carboxymethyl group, a 1-carboxyethyl group, a 3-carboxypropyl group or the like is exemplified as a preferable specific example. Specific examples of the case where Ri in the formula (2) is a phenyl group which is unsubstituted or substituted with a sulfo group, for example, an unsubstituted phenyl group; or a 2-sulfophenyl group or a 4-sulfobenzene group a phenyl group such as a 2,4-disulfophenyl group, a 3,5-disulfophenyl group or the like which has been subjected to a thiol group, wherein the number of the substituent is usually 1 i 4 , preferably 1 to 3, more Good for 1 to 2. A Ri in the above formula (2), preferably an unsubstituted C1 to C4 group or more preferably an unsubstituted phenyl group, is an unsubstituted C1 to C4 alkyl group. The specific example of Ri in the formula (2) is preferably a methyl group, an ethyl group, a n-propyl group, a tert-butyl group or a phenyl group, more preferably a methyl group, a n-propyl group or a styl group, and further preferably. It is a thiol group and a n-propyl group. 2 In the above formula (2), R 2 represents a cyano group, an aminomethyl group or a slow group. R is preferably all, but is preferably a cyano or amine-based base, more preferably a nitrogen-based oxime 2 as a combination of the formula (2) and R2, preferably R1 is a methyl group. The cyano group, or R1 is a methyl group and R2 is an amine f fluorenyl group. More preferably, the former is 19 201005048 In the above formula (7), Han 3 and r 4 each independently represent a gas atom, a gas atom, an exact group, an unsubstituted C1 to C4 alkyl group, or an unsubstituted 〇C4 alkoxy group. In the case where R and R4 in the formula (2) are unsubstituted a to the same, the (iv) group includes, preferably, the same as the above-mentioned unsubstituted C1 to C4 alkyl group. In the case where r and R4 in the formula (2) are unsubstituted η to a oxy group, the oxy group may be either a straight bond or a branched chain. Examples of 萁 include a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group: a n-butoxy group, a second butoxy group, and a third butoxy group. R3*R4 in the above formula (2) is more preferably a gas atom, a transverse group or an unsubstituted one of the above, and is preferably a specific example of R3 and C in the formula (7). a gas atom, a contiguous group, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a tributyl group, more preferably a hydrogen atom, a sulfo group, a methyl group, an isopropyl group, and further preferably a hydrogen atom or a sulfo group. R4R4 in the formula (2), particularly preferably an oxygen atom, a methyl group, and another 3, a combination of R3 and R4 is preferably a hydrogen atom and R4 is a sulfo group, or R3 is a sulfo group and R4 is a hydrogen atom. Preferably, the combination of the former is as follows: in the above formula (1), the ring substituted by R5 to RV is a benzene ring when the ring shown by the dotted line is not present, and a naphthalene ring when it is present in the ring shown by the broken line. The ring shown by the dotted line does not exist, that is, the substituted ring is a benzene ring. Preferably, 7 Vi A7 independently represents a group selected from the group consisting of: a gas atom; a gas atom; ; base group; amine base; amine 20 201005048 formazan; unsubstituted c 1~C4 alkyl; unsubstituted, or hydroxy, unsubstituted C1 to C4 alkoxy, hydroxy C1 The substituted C4 alkoxy, sulfo, carboxyl or alkoxy Ci~C4; unsubstituted or by a hydroxyl group, a sulfo group, a substituted carboxyl, or mono- or di-alkylamino C1~C4; without

取代，或者經羥基或羧基取代之C1〜C4烷基羰基胺基；未經取代’或者經經基、續基、或缓基取代之N'-Cl〜C4 院基腺基，未經取代’或者苯環經氣原子、未經取代之Ci 〜C4烷基、硝基、磺基、或綾基取代之苯基胺基；未經取代，或者苯環經氣原子、未經取代之C1〜C4貌基、硝基、績基、或羧基取代之苯甲酿基胺基；以及，未經取代，或者苯環經氣原子、未經取代之C1〜C4烷基、碗基、績基、或羧基取代之苯基磺醯基胺基。於R〜R7為未經取代之C1〜C4烷基之情形時，該烷基為直鏈、支鏈中之任一種均可，較佳為直鏈。作為未經取代之C1〜C4烷基之具體例，例如可列舉：甲基乙基、正丙基、正丁基等直鏈；異丙基、異丁基、第二丁基、第三丁基等支鏈。較佳的具體例為甲基或乙基，更佳為甲基。於式（2)中的R5〜RV為未經取代之幻〜以烷氧基^之情形時，該烷氧基包括較佳者在内，與上述…及"^4為未經取代之C 1〜C4烷氧基之情形相同即可。於於該烷氧基經羥基、未經取代之C1〜C4烷氧美、1 基C1〜CM烧氧基、續基、錢基取代之情形時 ^ 具體例，例如可„:2_經基乙氧基、Μ基 ·、、、經基丙氧㈣m基C1〜C4料基乙= 21 201005048 基乙氧基、正丙孰基乙氧基、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、正丙氧基丁氧基等未經取代之ci〜c4 烷氧基C1〜C4烷氧基；2_羥基乙氧基乙氧基等羥基。〜 C4烷氧| C1〜C4烷氧基;3_磺基丙氧基、4•磺基丁氧基等續基烷氧基；羧基甲氧基、2缓基乙氧基、％羧基丙氧基等羧基C1〜C4烷氧基等。Substituted, or C1~C4 alkylcarbonylamino group substituted by hydroxy or carboxy; unsubstituted 'or N'-Cl~C4 phenyl group substituted by a base, a contiguous group, or a slow group, unsubstituted' Or a phenylamine group substituted by a gas atom, an unsubstituted Ci~C4 alkyl group, a nitro group, a sulfo group or a fluorenyl group; unsubstituted or a benzene ring via a gas atom, unsubstituted C1 to C4 a benzyl, phenyl, or carboxy substituted benzylamino group; and, unsubstituted, or a benzene ring via a gas atom, an unsubstituted C1 to C4 alkyl group, a bowl base, a base, or a carboxy-substituted phenylsulfonylamino group. In the case where R to R7 are an unsubstituted C1 to C4 alkyl group, the alkyl group may be either a straight chain or a branched chain, and is preferably a straight chain. Specific examples of the unsubstituted C1 to C4 alkyl group include a straight chain such as methylethyl, n-propyl or n-butyl; isopropyl, isobutyl, t-butyl and tert-butyl; Base and other branches. A preferred specific example is a methyl group or an ethyl group, more preferably a methyl group. In the case where R5 to RV in the formula (2) is an unsubstituted phantom to an alkoxy group, the alkoxy group includes the above, and the above... and "^4 are unsubstituted. The case of C 1 to C 4 alkoxy groups may be the same. In the case where the alkoxy group is substituted with a hydroxyl group, an unsubstituted C1 to C4 alkoxy group, a 1 group C1 to CM alkoxy group, a hydrazine group, or a thiol group, a specific example can be exemplified, for example, Ethoxy, fluorenyl, and, propyl propyl (tetra) m-based C1 to C4. Group B = 21 201005048 ethoxy, n-propyl ethoxy, isopropoxy ethoxy, n-butoxy Unsubstituted ci~c4 alkane such as ethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy Oxyl C1~C4 alkoxy; 2-hydroxylethoxyethoxy, etc. hydroxy.~C4 alkoxy; C1~C4 alkoxy; 3_sulfopropoxy, 4 sulfobutoxy, etc. Alkoxy group; a carboxyl group C1 to C4 alkoxy group such as a carboxymethoxy group, a 2-sulfoethoxy group or a % carboxypropoxy group.

於式（2)中的R5〜R7為未經取代之單或二以〜以烷基胺基之情形時，該C1〜C4烷基部分為直鏈或支鏈中之任一種均可。作為其具體例，可列舉：甲胺基、乙胺基、正丙胺基、異丙胺基、正丁胺基、二甲胺基、二乙胺基、一正丙胺基、二正丁胺基等直鏈；第二丁胺基、第三丁胺基、一異丙胺基等支鍵等。於該單或二C1〜C4烷基胺基，經羥基、磺基、或叛基取代之情形時，作為其具體例，例如可列舉：2羥基乙胺基、2-羥基丙联基' 2,2，-二羥基二乙胺基等經羥基取代之單或一 C1〜C4炫基胺基;2-績基乙胺基、3-確基丙胺基、4-磺基丁胺基、3,3’-二確基二丙胺基等經磺基取代之單或二C1〜C4烧基胺基；缓基甲胺基、2-羧基乙胺基、3-缓基丙胺基、2,2'-二羧基二乙胺基等經羧基取代之單或二 C1〜C4烷基胺基等。於式（2)中的R5〜R7為未經取代之C1〜C4烷基羰基胺基之情形時’該C1〜C4烷基部分可為直鏈或支鏈中之任一種’較佳為直鏈者。作為具體例，可列舉乙醯基胺基、 22 201005048 丙酿基胺基、丁醯基胺基等。於該ci〜C4烷基羰基胺基經羥基或羧基取代之情形時’作為該C1〜C4烷基羰基胺基之具體例，例如可列舉：經基乙酿基胺基、2-羥基丙醯基胺基、4-羥基丁醯基胺基等經基C1〜C4烷基羰基胺基；3-羧基丙醯基胺基等竣基 C1〜C4烷基羰基胺基等。於式（2)中的R5〜R7為基脲基之情形時，與未經取代相比，較佳為具有取代基者。於該N，-C1〜C4烷基脲基經羥基、磺基、或羧基取代之情形時’作為其具體例，例如可列舉：Ν·-2-羥基乙基脲基、Ν，-3·經基乙基腺基等Ν.，基以〜以烷基腺基；nIn the case where R5 to R7 in the formula (2) are unsubstituted mono- or di- to-alkylamino group, the C1 to C4 alkyl moiety may be either linear or branched. Specific examples thereof include a methylamino group, an ethylamino group, a n-propylamino group, an isopropylamine group, a n-butylamino group, a dimethylamino group, a diethylamino group, a n-propylamino group, a di-n-butylamino group, and the like. Straight chain; a second butylamine group, a third butylamine group, a monoisopropylamine group or the like. In the case where the mono- or di-C1 to C4 alkylamino group is substituted by a hydroxyl group, a sulfo group or a thiol group, specific examples thereof include a 2-hydroxyethylamino group and a 2-hydroxypropyl group '2 a 2,-dihydroxydiethylamino group or the like substituted by a hydroxy group, or a C1 to C4 danyl group; 2-exetylethylamino, 3-decylamino, 4-sulfobutylamino, 3 a mono- or di-C1-C4 alkylamino group substituted by a sulfo group such as 3'-di-di-dipropylamino group; a thiomethylamino group, a 2-carboxyethylamino group, a 3-hydroxypropylamino group, 2, 2 a mono- or di-C1-C4 alkylamino group substituted by a carboxyl group such as a 'dicarboxydiethylamine group. In the case where R5 to R7 in the formula (2) are an unsubstituted C1 to C4 alkylcarbonylamino group, the C1 to C4 alkyl moiety may be either a straight chain or a branched chain, preferably straight. Chain. Specific examples thereof include an ethenylamino group, 22 201005048 propylamino group, and butyl sulfhydryl group. In the case where the ci~C4 alkylcarbonylamino group is substituted by a hydroxyl group or a carboxyl group, 'specific examples of the C1 to C4 alkylcarbonylamino group include, for example, a mercaptoamine group and a 2-hydroxypropionate group. A mercapto group such as a C1-C4 alkylcarbonylamino group such as a hydroxy group or a 4-hydroxybutanylamino group; a C1 to C4 alkylcarbonylamino group such as a 3-carboxypropylamino group; In the case where R5 to R7 in the formula (2) are a ureido group, it is preferred to have a substituent as compared with the unsubstituted. In the case where the N,-C1 to C4 alkylureido group is substituted with a hydroxyl group, a sulfo group or a carboxyl group, 'specific examples thereof include, for example, anthracene-2-hydroxyethylureido group, anthracene, -3· By a base ethyl gland group, etc., the base is ~ to an alkyl gland; n

Φ 磺基乙基脲基、:K，-3-磺基丙基脲基等Ν·_磺基Cl〜c4烷基腺基；N·-缓基甲基腺基、N，_2遗基乙基腺基、^錢^ 基腺基、N，·續基丁基腺基•德基^〜以隸腺基等< 於式（2)中的R5〜R7為以如下順序記載而分別具有取代基之苯基胺基、苯甲醯基胺基、或苯基續醯基胺基，並且各基中所含之苯環的取代展盔丞為C1〜C4、烷基之情形時，該院基為直鏈、支鏈、或環壯_士义哀狀中之任一種均可，較佳為直鏈或支鏈者。作為具體例，例^1 灼如可列舉：甲基、乙基、正丙基、正丁基等直鏈；異丙基、s 異丁基、第二丁基、第三丁基等支鏈者。取代或者苯環經氣原子、 '續基、或羧基取代之笨 ’例如可列舉：未經取代於式（2)中的R5〜R7為未經未經取代之C1〜C4烷基、硝基基胺基之情形時’作為其具體例 23 201005048 之苯基胺基’或者2-氣苯基胺基、4_氣苯基胺基、2,4-二氯笨基胺基等經氣原子取代之苯基胺基；2-甲基苯基胺基、 4-曱基苯基胺基、4_第三丁基苯基胺基等經未經取代之c i 〜C4烷基取代之苯基胺基；2-硝基苯基胺基、4-硝基笨基胺基等經硝基取代之苯基胺基；3-磺基苯基胺基、4-磺基笨基胺基、2,4-二磺基苯基胺基、3,5-二磺基苯基胺基等經項基取代之苯基胺基；2-叛基苯基胺基、4-叛基苯基胺基、 _ 2,5-二羧基苯基胺基、3，5-二羧基苯基胺基等經羧基取代之苯基胺基等。於式（2)中的R5〜R7為未經取代或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基、或羧基取代之苯曱醯基胺基之情形時，作為其具體例，例如可列舉：未經取代之苯甲醯基胺基，或2-氣苯甲醯基胺基、4_氣苯曱醯基胺基、2,4 -一氣本基胺基等經氣原子取代之苯曱醯基胺基；2-甲基苯曱醯基胺基、3-曱基苯曱醯基胺基、4_甲基苯 • 甲醯基.胺基等經C1〜C4烷基取代之苯曱酿基胺基；2_硝基，苯甲醢基胺基、4-墙基苯甲酿基胺基> 3,5-二硝基笨甲醯基胺基等經硝基取代之苯甲醯基胺基；2_磺基苯甲酿基胺基、4-磺基苯甲酿基胺基等經磺基取代之苯甲醯基胺基； 2-羧基苯甲醯基胺基、4-羧基苯曱醯基胺基、3,5-二羧基苯甲醯基胺基等經羧基取代之苯甲醯基胺基等。於式（2 )中的R5〜R7為未經取代或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基、或叛基取代之苯基磺醯基胺基之情形時，作為其具體例，例如可列舉：未 24 201005048 經取代之苯基磺酿基胺基，或2-氣苯基磺醯基胺基、‘氣苯基磺醢基胺基等經氣原子取代之苯基磺醯基胺基；2-曱基笨基磺醯基胺基、4-甲基苯基磺醯基胺基、4-第三丁基苯基磺醯基胺基等經C1〜C4烷基取代之苯基磺酿基胺基；2 -硝基苯基績酿基胺基、3-·®肖基苯基績酿基胺基、4-硝基苯基磺醯基胺基等經硝基取代之苯基磺醯基胺基；3-磺基苯基磺醯基胺基、4-磺基苯基磺醯基胺基等經磺基取代之苯基磺醯基胺基；3-羧基苯基磺醯基胺基、4-羧基苯 '· 基磺酿基胺基等經羧基取代之苯基磺醯基胺基等。式（2)中的R5至R7之具體例較佳為：氫原子、羧基、磺基、甲基、乙基、甲氧基、乙氧基、2-羥基乙氧基、2-磺基乙氧基、3-磺基丙氧基、4-磺基丁氧基、羧基甲氧基、 2-敌基乙氧基、甲胺基、乙胺基、2-經基乙胺基.、2-續基乙胺基、3·磺基丙胺基、2-羧基乙胺基、二曱胺基、二乙胺基、2,2’-二羥基二乙胺基、2,2’-二羧基二乙胺基、3,3’-二 Ο 磺基二丙胺基、乙醢基胺基、3-羧基丙醯基胺基、4-羥基 - 丁醯基胺基、N·-羧基甲基脲基、Ν·-2-磺基乙基脲基、4-磺基苯基胺基、2,4-二磺基苯基胺基、2,5-二羧基苯基胺基、苯甲醯基胺基、3-磺基苯甲醯基胺基、2-羧基苯甲醯基胺基、苯基磺醯基胺基、4-甲基笨基磺醯基胺基、4-硝基苯基磺醯基胺基、3-磺基苯基磺醯基胺基、4-羧基苯基磺醢基胺基等，更佳為：氫原子、磺基、甲基、甲氧基、2-羥基乙氧基、2-磺基乙氧基、3-磺基丙氧基、4-磺基丁氧基、二甲胺基、3,3’-二磺基二丙胺基、乙醯基胺基、3-羧基丙 25 201005048 酿基胺基、N磺基乙基脲曱醯基胺基、4_f 4基胺基、苯甲基本基磺醯基胺基，進而子、績基、曱基、甲氧基、34基丙氧基。為.氯原式.（2)中的尺5至兑7+4人 A至11之組合，較佳為為續基丙氧基戈續基丁氧基，更佳兔2选贫工片好 R6為Μ…… 或磺基丁氧基；真’、，為氫原子、氣原子、乙酿基胺基、甲基或乙基、甲，基或乙氣基、或者確基丙氧基或績基丁氧基" '· 另6外’ R至R7之組合，進而較佳為：尺5為績基丙氧基； R為氫原子；R、甲基、甲氧基、氣原子、或者乙酿基胺基。上述式（2)中，尺8至Rl0所取代之環，分別於虛線所示之環並不存在時表示苯環，於虛線所示之環存在時表示萘環其中較佳為虛線所示之環並不存在，亦即，較佳為 R至R。所取代之環為苯環。 R至R1G分別獨立表示選自由下述所構成之群组之 • 基：氫原子；氣原子；經基；續基；叛基；胺績醯基；胺 • 甲醯基；未經取代之C1〜C4烷基；未經取代，或者經經基、C1〜C4烷氧基、羥基C1〜C4烷氧基、磺基、或羧基取代之C1〜C4烷氧基；經羥基、磺基、或羧基取代之C1 〜C4垸硫基；未經取代，或者經羥基、磺基、或羧基取代之單或二C1〜C4烷基胺基；未經取代，或者經羥基或羧基取代之C1〜C4烷基幾基胺基；未經取代，或者經羥基、續基、或羧基取代之N'-Cl〜C4烷基脲基；未經取代，或者苯環經氣原子、C1〜C4烷基、硝基、磺基、或羧基取代 26 201005048 之苯基胺基；未經取代，或者笨環經氣原子、未經取代之 C1〜C4烧基、硝’基、確基、或緩基取代之笨甲醯基胺基；、及未、差取代&者笨環經氣原子、未經取代之c ^〜以燒基“肖基、續基、或㈣取代之苯基俩基胺基。於R8〜R1。為未經取代之C1〜C4烷基之情形時，該烷基為直鍵、支鍵中之/f壬_ ^ 1 種均可’較佳為直鏈。作為未經Φ sulfoethylureido, K,-3-sulfopropylureido, etc. Ν _ sulfo-Cl~c4 alkyl gland; N·-sulfomethyl gland, N, _2 The basal gland group, the hydroxy group, the aryl group, the N, the butyl group, the butyl group, the thiol group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group, the aryl group When the substitution of the phenylamine group, the benzhydrylamino group, or the phenyl fluorenylamino group, and the substitution of the benzene ring contained in each group is C1 to C4, an alkyl group, The base of the hospital may be any of a straight chain, a branch, or a ring, or a straight chain or a branched chain. As a specific example, examples include a straight chain such as a methyl group, an ethyl group, a n-propyl group or a n-butyl group; and a branched chain such as an isopropyl group, an s-isobutyl group, a second butyl group and a third butyl group; By. The substituted or benzene ring may be exemplified by a gas atom, a 'renewing group, or a carboxy group substituted'. For example, R5 to R7 which are unsubstituted in the formula (2) are unsubstituted C1 to C4 alkyl groups, and a nitro group. In the case of an amino group, the phenylamino group as a specific example 23 201005048 or a 2-atomylphenyl group, a 4-phenylphenylamino group, a 2,4-dichlorophenylamino group or the like Substituted phenylamino; 2-methylphenylamino, 4-nonylphenylamino, 4-tert-butylphenylamino, etc., unsubstituted ci~C4 alkyl substituted phenyl a nitro group substituted with a nitro group such as a 2-nitrophenylamino group or a 4-nitrophenylamino group; a 3-sulfophenylamino group, a 4-sulfophenylamino group, 2 a phenylamino group substituted with a 4-disulfophenylamino group, a 3,5-disulfophenylamino group, or the like; a 2-refenylphenylamino group, a 4-repentylphenylamino group a carboxy-substituted phenylamine group such as _ 2,5-dicarboxyphenylamino group or 3,5-dicarboxyphenylamino group. When R5 to R7 in the formula (2) are unsubstituted or a phenyl ring is substituted by a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group or a carboxyl group; As a specific example thereof, for example, an unsubstituted benzhydrylamino group, or a 2-gas benzoguanidino group, a 4-benzotrienyl group, a 2,4-dimethylamine group, a phenylhydrazine group substituted with a gas atom; a 2-methylphenylhydrazino group, a 3-mercaptophenylhydrazino group, a 4-methylbenzene group, an onylidene group, an amine group, etc. C1-C4 alkyl-substituted benzoquinone-based amine; 2-nitro group, benzhydrylamino group, 4-wall-based benzoylamino group> 3,5-dinitrobenzamide a sulfonyl-substituted benzhydrylamine group; a 2-sulfobenzoylamino group; a 4-sulfobenzoylamino group; A carboxyl group-substituted benzhydrylamino group such as a carboxybenzylideneamino group, a 4-carboxyphenylmercaptoamine group, or a 3,5-dicarboxybenzimidyl group. R5 to R7 in the formula (2) are unsubstituted or phenyl ring via a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group or a thiol-substituted phenylsulfonylamino group. In the case, as a specific example, for example, a substituted phenylsulfonylamino group, a 2-phenylphenylsulfonylamino group, or a gas phenylsulfonylamino group, which is not substituted for 24 201005048, may be mentioned. Atomic substituted phenylsulfonylamino group; 2-mercaptosylsulfonylamino group, 4-methylphenylsulfonylamino group, 4-tert-butylphenylsulfonylamino group, etc. C1-C4 alkyl-substituted phenylsulfonic acid amine; 2-nitrophenyl-alkylamino, 3-·® Schottylphenyl-based amine, 4-nitrophenylsulfonyl A sulfo group-substituted phenylsulfonylamino group such as an amine group or the like which is substituted with a nitro group; a 3-sulfophenylsulfonylamino group; a 4-sulfophenylsulfonylamino group; A carboxyl group-substituted phenylsulfonylamino group such as an amino group; a 3-carboxyphenylsulfonylamino group; a 4-carboxybenzene'-sulfonylamino group; Specific examples of R5 to R7 in the formula (2) are preferably a hydrogen atom, a carboxyl group, a sulfo group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a 2-hydroxyethoxy group or a 2-sulfoethyl group. Oxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboethoxy, methylamino, ethylamino, 2-ethylethylamino., 2 - Continuation of ethylamine, 3, sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2,2'-dihydroxydiethylamino, 2,2'-dicarboxy Diethylamino, 3,3'-dioxalyldipropylamino, ethyl hydrazino, 3-carboxypropylamino, 4-hydroxy-butenylamino, N-carboxymethylureido, Ν·2-sulfoethylureido, 4-sulfophenylamino, 2,4-disulfophenylamino, 2,5-dicarboxyphenylamino, benzhydrylamino , 3-sulfobenzylideneamino, 2-carboxybenzylidenylamine, phenylsulfonylamino, 4-methylphenylsulfonylamino, 4-nitrophenylsulfonate Amino group, 3-sulfophenylsulfonylamino group, 4-carboxyphenylsulfonylamino group, etc., more preferably: hydrogen atom, sulfo group, methyl group, methoxy group, 2-hydroxyethoxy group 2-sulfoyl Oxyl, 3-sulfopropoxy, 4-sulfobutoxy, dimethylamino, 3,3'-disulfodipropylamino, ethionylamino, 3-carboxypropyl 25 201005048 Amino, N-sulfoethyl urea sulfhydryl, 4_f 4 ylamino, benzyl sulfonylamino, phenyl, decyl, decyl, methoxy, 34 propylpropoxy. It is a combination of the ruler 5 and the 7+4 person A to 11 in the formula (2), preferably a thiol methoxy contigyl butoxy group, and a better rabbit 2 R6 is Μ... or sulfobutoxy; true ', is a hydrogen atom, a gas atom, an ethylamino group, a methyl or ethyl group, a methyl group or an ethyl group, or a decyloxy group or A combination of R and R; '· another 6 external' R to R7, and further preferably: the rule 5 is a propyloxy group; R is a hydrogen atom; R, a methyl group, a methoxy group, a gas atom, Or an ethylamine group. In the above formula (2), the ring substituted by the rule 8 to R10 represents a benzene ring when the ring shown by a broken line does not exist, and the ring represented by a broken line indicates that the naphthalene ring is preferably a dotted line. The ring does not exist, that is, preferably R to R. The ring substituted is a benzene ring. R to R1G each independently represent a group selected from the group consisting of: a hydrogen atom; a gas atom; a radical; a contig; a thiol; an amine; an amine; a fluorenyl; an unsubstituted C1 a C1 to C4 alkoxy group which is unsubstituted or substituted with a thiol group, a C1 to C4 alkoxy group, a hydroxy C1 to C4 alkoxy group, a sulfo group or a carboxyl group; a C1-C4 thiol group substituted by a carboxyl group; a mono- or di-C1-C4 alkylamino group which is unsubstituted or substituted with a hydroxy group, a sulfo group or a carboxyl group; an unsubstituted or substituted C1 to C4 group which is substituted by a hydroxyl group or a carboxyl group Alkylaminoamino; unsubstituted, or N'-Cl~C4 alkylureido substituted by hydroxy, contiguous, or carboxy; unsubstituted, or phenyl ring via a gas atom, C1 to C4 alkyl, Nitro, sulfo, or carboxy substituted 26 phenylamino group of 2010 201048; unsubstituted, or a stupid ring of a gas atom, an unsubstituted C1 to C4 alkyl group, a nitrate' group, an exact group, or a slow group Stupidylaminol group; and unsubstituted, poorly substituted & a stupid ring of a gas atom, unsubstituted c ^ ~ to burn base "Schocchi, contiguous, or (d) Phenylamino group. In the case of R8 to R1. In the case of an unsubstituted C1 to C4 alkyl group, the alkyl group is a straight bond, and /f壬_^1 of the bond may be preferred. Straight chain

取代之C1〜C4燒基之具體例，例如可列舉：甲基、乙基、正丙基、正丁基等直鏈；異丙基、異丁基、第二丁基第三丁基等支鏈。較佳的具體例為甲基或乙基，更佳為甲基。於式（2)中的r〜Rio為未經取代之c卜Q烷氧基之情形時，該烷氧基包括較佳者在内，與上述尺3及尺4為未經取代之Cl〜C4烷氧基之情形相同即可。於該烧氧基經經基、未經取代之C1〜C4烧氧基、經基C卜C4院氧基、續基、或㈣取代之情形時，作為其具體例’例如可列舉：2_羥基乙氧基、2_羥基丙氧基、3_ 羥基丙氧基等羥基C1〜C4燒氧基；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、甲驗丙&基、6氧基丙輕、正丙氧基丙氧基、異丙氧基丁氧基、正丙氧基丁氧基等未經取代之ci〜 c4 烷氧基Cl〜C4烷氧基；2-羥基乙氧基乙氧基等羥基ci〜 C4烷氧基C1〜 C4烷氧基；3_磺基丙氧基、4磺基丁氧基等磺基C〗〜C4烷氧基，·羧基，氧基、2_羧基乙氧基、3: 羧基丙氧基等羧基C1〜C4烷氧基等。烷硫基於式（2)中的R8〜R10為未經取代之C1〜c4 27 201005048 之情形時，該C1〜C4燒基部分為直鍵、支鍵中之任一種均佳。作為其具體例’例如可列舉：甲硫基、乙硫基、正丙硫基、異丙硫基、正丁硫基、二甲硫基、二乙硫基、二 ^丙硫基、二正丁硫基等直鏈；第二丁硫基、第三丁硫基、一異丙硫基等支鍵等。，於該單或二C1〜C4燒硫基經減、續基、或幾基取代之清形時’作為其具體例’例如可列舉：2A基乙硫基、 'φ 羥基丙硫基、2,2’-二羥基二乙硫基等經羥基取代之單或一 C1〜C4烷硫基；2_磺基乙硫基、3磺基丙硫基、4磺基丁硫基3，3 _ 一崎基二丙硫基等經磺基取代之單或二以〜 C4 ,烧硫基；缓基甲硫基、2_羧基乙硫基、％羧基丙硫基、 2,2 _—羧基二乙硫基等經羧基取代之單或二ci〜c4烷硫基等。於式（2)中的R8〜Ri〇為未經取代之單或二ci〜c4 院基胺基之情形時，言亥C1〜C4院基部分為直鏈或支鍵中 ® 之任一種均可。作為其具體例，可列舉：甲胺基、乙胺基、 . 正丙胺基、異丙胺基、正丁胺基、二甲胺基、二乙胺基、二正丙胺基、二正丁胺基等直鏈;第二丁胺基第三丁胺基、二異丙胺基等支鏈等。於該單或二C1〜C4烷基胺基經羥基、磺基、或魏基取代之情形時’作為其具體例，例如可列舉：2_羥基乙胺土經基丙胺基、2,2 -—經基一己胺基等經經基取代之單或二C1〜C4烷基胺基;2_磺基乙胺基、3_磺基丙胺基、 4-磺基丁胺基、3,3，_二磺基二丙胺基等經磺基取代之單或 28 201005048 二Cl〜C4烷基胺基；羧基甲胺基、2_綾基乙胺基、3羧基丙胺基、2,2’-二羧基二乙胺基等經羧基取代之單或二a C4烷基胺基等。於式（2)中的R«〜為未經取代之^〜以烷基羰基胺基之情形時，該C1〜C4烷基部分可為直鏈或中之任一種，較佳為直鏈者》作為具體例，可列舉乙酿基胺基、丙醯基胺基、丁醯基胺基等。 φ 於該C1〜C4烷基羰基胺基經羥基或羧基取代之情形時，作為該C1〜C4烷基羰基胺基之具體例，例如可列舉：羥基乙醯基胺基、2-羥基丙醯基胺基、4_羥基丁醯基胺基等羥基C1〜C4烷基羰基胺基；3_羧基丙醯基胺基等羧基 C1〜C4烷基羰基胺基等。於式（2)中的R8〜Rm為斤—以〜以烷基脲基之情形時，與未經取代相比，較佳為具有取代基·者。於該N’_C1〜C4烷基脲基經羥基、磺基、或羧基取代參之情形時’作為其具體例，例如可列舉：N'-2-經基乙基腺 * 基、N’_3_羥基乙基脲基等N，-羥基C1〜C4烷基脲基；Ν，-2· 磺基乙基脲基、Ν·-3-磺基丙基脲基等Ν，_磺基C1〜C4烷基脲基；Ν·-羧基甲基脲基、N，_2_羧基乙基脲基、N，_3_羧基丙基脲基、N'-4-羧基丁基脲基等N，-羧基C1〜C4烷基脲基等。於式（2 )中的R〜R10為以如下順序記載而分別具有取代基之苯基胺基、苯甲醯基胺基、或苯基磺醯基胺基，並且各基中所含之苯環的取代基為c丨〜C4烷基之情形時’該燒基為直鏈、支鍵、或環狀中之任一種均可，較佳 29 201005048 為直鏈或支鏈者。作為具體例，例如可列舉：甲基、乙基、正丙基、正丁基等直鏈；異丙基、異丁基第二丁基第三丁基等支鏈者。於式（2 )中的r8〜RiQ為未經取代或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基、或羧基取代之苯 • 基胺基之情形時，作為其具體例，例如可列舉：未經取代 .之苯基胺基’或者2·氣苯基胺基、4-氣笨基胺基、2,4_二氣 « 苯基胺基等經氣原子取代之苯基胺基；2·曱基苯基胺基、 4曱基笨基胺基、4-第二丁基笨基胺基等經未經取代之C1 〜C4烷基取代之苯基胺基；2_硝基笨基胺基、‘硝基苯基胺基等經硝基取代之苯基胺基；3_磺基苯基胺基、4磺基苯基胺基、2,4-二磺基苯基胺基、3,5-二磺基苯基胺基等經磺基取代之苯基胺基；2-羧基苯基胺基、4_羧基苯基胺基、 2,5-二羧基苯基胺基、3,5-二羧基笨基胺基等經羧基取代之· 苯基胺基等。 ® 於式（2 )中的R〜R1G為未經取代或者苯環經氣原子、 * 未經取代之C1〜C4燒基、硝基、磺基、或羧基取代之笨甲酿基胺基之情形時’作為其具體例，例如可列舉：未經取代之笨甲酿基胺基，或2-氣苯甲醯基胺基、4_氯苯甲醯基私:基、2,4-二氯笨基胺基等經氯原子取代之苯甲醢基胺基，2 -甲基苯甲酿基胺基、3 -曱基笨曱酿基胺基、4_曱基苯甲醯基胺基等經C1〜C4烷基取代之苯甲醯基胺基；2_硝基笨甲醯基胺基、4-硝基苯甲醯基胺基、3,5_二硝基苯甲醯基胺基等經破基取代之苯甲醯基胺基；2_續基苯甲醯基胺 30 201005048 基4磺基苯甲醯基胺基等經磺基取代之苯甲醯基胺基； 2-羧基苯甲醯基胺基、4_羧基苯甲醯基胺基、3,5_二羧基苯甲醯基胺基等經羧基取代之苯甲醯基胺基等。於式（2)中的R8〜為未經取代或者苯環經氣原子、未經取代之C1〜C4烷基、硝基、磺基、或羧基取代之笨基碩醯基胺基之情形時，作為其具體例，例如可列舉：未經取代之苯基磺醯基胺基，或2·氣苯基磺醯基胺基、4_氣謇笨基績酿基胺基等經氣原子取代之苯基磺醢基胺基；2_甲基苯基續醯基胺基、4-甲基苯基磺醯基胺基、4_第三丁基笨基磺醯基胺基等經C1〜C4烷基取代之笨基磺醯基胺基；2-硝基苯基磺醯基胺基、3_硝基笨基磺醯基胺基、4_ 確基苯基磺醯基胺基等經硝基取代之苯基磺醯基胺基；3_ 項基苯基磺醯基胺基、4-磺基苯基磺醯基胺基等經磺基取代之苯基磺醯基胺基；3-羧基苯基磺醯基胺基、4-羧基笨基磺醯基胺基等經羧基取代之苯基磺醯基胺基等。 # 式（2)中的R8至R10之具體例，較佳為：氫原子、 . 氣原子、羧基、磺基、甲基、乙基、甲氧基、乙氧基、2- 羥基乙氧基、2-磺基乙氧基、3-磺基丙氧基、4-磺基丁氧基、羧基甲氧基、2-羧基乙氧基、甲胺基、乙胺基、2-羥基乙胺基、2-磺基乙胺基、3-磺基丙胺基、2-羧基乙胺基、二甲胺基、二乙胺基、2,2'-二羥基二乙胺基、2,2’-二羧基二乙胺基、3,3'-二磺基二丙胺基、乙醯基胺基、3-羧基丙醯基胺基、4-羥基丁醯基胺基、Ν’-羧基甲基脲基、N’-2-磺基乙基脲基、4-磺基苯基胺基、2,4-二磺基苯基胺基、2,5-二羧 31 201005048 基苯基胺基、笨甲醯基胺基、3_磺基苯甲醯基胺基、2_羧基苯甲酿基胺基、苯基磺醯基胺基、4_曱基笨基磺醯基胺基、4-硝基苯基磺醯基胺基、3_磺基苯基磺醯基胺基、4_ 羧基苯基磺醯基胺基等，更佳為：氫原子、氣原子、磺基、甲基、甲氧基、2-經基乙氧基、2-橫基乙氧基、3_續基丙氧基、4-磺基丁氧基、二甲胺基、3,3，·二磺基二丙胺基、乙酿基胺基、3-竣基丙醢基胺基、ν，·μ基乙基脲基、2,4_ 二續基苯基胺基、苯甲醯基胺基、4·甲基苯基雜基胺基，進而較佳為：氫原+、績基、甲基、甲氧基、3_續基丙氧基。式（2)中的R8至R1。之組合，較佳為：尺8為磺基丙硫基或4基T硫基，較佳為Μ基丙硫基或4_確基丁硫基更佳為項基丙硫基；R9為氫原子；R10為氣原子、乙 =基胺基、甲基或乙基、甲氧基或乙氧基、或者績基丙氧土，較佳為氣原子、乙醯基胺基、甲 V, 、或甲氧基，更佳為氣原子β 由上述式（2)所示之化合物的較佳者，係由上述式⑷ 所不之化合物。式（4)中’基A、r1。、及…至Ri。所取代之j哀，包括由虛線所示之環，^ 鱼衣包括較佳者等在内，興上述式（2)相同即可。由上述式（4)所示之化合物的鲂祕一較佳者’係由上述式（5 ) 所不之化合物。式（5)中，基A , 辇# R至R ’包括較佳者寻在内，與上述式（4)相同即可。 R及R7分別獨立表示氫原子 ’氯原子；未經取代，或 32 201005048 者經羥基或羧基取代之Cl〜C4烷基羰基胺基；未經取代之C1〜C4烷基，或是，未經取代，或者經磺基或羥基取代之C1〜C4烧氧基；R6表示氫原子。 R至R分別獨立表示氫原子；氯原子；未經取代，或者經羥基或羧基取代之C1〜C4烷基羰基胺基；磺基ci 〜C4烧氧基；未經取代之C1〜C4烧基；未經取代，或者經續基取代之C1〜C4垸氧基；或是，經績基或叛基取代之C1〜C4烷硫基；R9表示氫原子。式（5)中的…至R〗〇, 包括較佳者在内’與上述式⑴中的r8& r1〇中的相當者相同即可》上述式（2)、（4)及（5)中 (6 )所表不之基。於上述式⑷中n〆分別獨立表示選自由_ 述所構成之群組中之基：氫原子；氣原子；磺基；硝基經基；胺伽基；未經取代，或者經㈣、未經取代之c 〜C4烧氧基、磺基、或缓基取代之C1〜C4燒氧基.以2 未經取代，或者經羥基、磺基、或綾基取代之ci〜’ 4 / 基續醯基。 .. _ $ 於式⑷中的R"至C為未經取代或者經」經取代之cn〜㈣氧基、«、或_取代之ci〜\ 氧基之情科，該院氧基包括較佳者在内， } 中的R5及R7中的C1〜C4燒氧基相當者相同即可（2 於式…中的R"H"為未經取美基、緣基取代之m〜CU基伽基之情形時== 33 201005048 具體例，例如可列舉：曱基磺醯基、乙基磺醯基、丙基磺醯基、異丙基磺醯基、正丁基磺醯基、第二丁基磺醯基、第三丁基磺醯基等直鏈或支鏈的未經取代之C1〜C4烷基磺醯基；2-羥基乙基磺醯基、3-羥基丙基磺醯基等羥基C1 〜C4烷基磺醯基；2-磺基丙基磺醯基、3-磺基丙基磺醯基、 4-磺基丁基磺醯基等磺基ci〜C4烷基磺醯基；羧基曱基磺Specific examples of the substituted C1 to C4 alkyl group include a straight chain such as a methyl group, an ethyl group, a n-propyl group or a n-butyl group; and an isopropyl group, an isobutyl group, a second butyl group and the like. chain. A preferred specific example is a methyl group or an ethyl group, more preferably a methyl group. In the case where r to Rio in the formula (2) is an unsubstituted c-Q alkoxy group, the alkoxy group includes a preferred one, and the above-mentioned ruler 3 and rule 4 are unsubstituted Cl~. The case of the C4 alkoxy group is the same. In the case where the alkoxy group is substituted by a trans group, an unsubstituted C1 to C4 alkoxy group, a group C, a C4 alkoxy group, a contiguous group or a (4), as a specific example thereof, for example, 2_ Hydroxy C1~C4 alkoxy groups such as hydroxyethoxy, 2-hydroxypropoxy or 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropyl Oxyethoxy, n-butoxyethoxy, acetoin & yl, hexaethoxypropan, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy Such as unsubstituted ci~ c4 alkoxy Cl~C4 alkoxy; 2-hydroxyethoxyethoxy and the like hydroxy ci~ C4 alkoxy C1~C4 alkoxy; 3 sulfopropoxy, a sulfo group such as a sulfobutoxy group such as a sulfo group, a carboxyl group such as a C4 alkoxy group, a carboxyl group, an oxy group, a 2-carboxyl ethoxy group or a carboxypropoxy group; and a carboxy C1 to C4 alkoxy group. When the R8 to R10 in the formula (2) are unsubstituted C1 to c4 27 201005048, the C1 to C4 alkyl group is preferably a straight bond or a bond. Specific examples thereof include, for example, a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a n-butylthio group, a dimethylthio group, a diethylthio group, a dipropylthio group, and a di-n-butyl group. a straight chain such as a butylthio group; a bond such as a second butylthio group, a third butylthio group or an isopropylthio group; and the like. When the mono- or di-C1 to C4-sulfuryl group is subjected to a subtraction, a continuation, or a radical substitution, 'as a specific example thereof', for example, 2A ethylthio group, 'φ hydroxypropylthio group, 2 , 2'-dihydroxydiethylthio group or the like substituted by a hydroxy group, or a C1 to C4 alkylthio group; 2-sulfoethylthio group, 3 sulfopropylthio group, 4 sulfobutylthio group 3,3 _ Monosyl-dipropylthio-substituted sulfo-substituted mono- or di- to-C4, sulfur-based; thiomethylthio, 2-carboxyethylthio, %carboxypropylthio, 2,2-carboxyl a single or two ci~c4 alkylthio group substituted by a carboxyl group such as an ethylthio group. When R8~Ri〇 in the formula (2) is an unsubstituted mono- or di-ci-c4-based amine group, the C1 to C4-based part of the formula is linear or branched. can. Specific examples thereof include a methylamino group, an ethylamino group, a n-propylamino group, an isopropylamine group, a n-butylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, and a di-n-butylamino group. Or a straight chain; a branched chain such as a second butylaminobutylidene group or a diisopropylamine group. In the case where the mono- or di-C1-C4 alkylamino group is substituted by a hydroxyl group, a sulfo group or a thiol group, 'as a specific example thereof, for example, 2-hydroxyethylamine-based propylamino group, 2,2- a mono- or di-C1-C4 alkylamino group substituted by a radical such as a hexylamino group; 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, 3, 3, _Disulfodipropylamino group or the like substituted by sulfo group or 28 201005048 DiCl~C4 alkylamino group; carboxymethylamino group, 2-mercaptoethylamino group, 3-carboxypropylamino group, 2,2'-dicarboxyl group A mono- or di-a C4 alkylamino group substituted by a carboxyl group such as a diethylamine group. When R«~ in the formula (2) is an unsubstituted alkylcarbonylamino group, the C1 to C4 alkyl moiety may be either a straight chain or a linear one, preferably a linear one. As a specific example, an ethyl arylamino group, a propyl fluorenyl group, a butyl fluorenyl group, etc. are mentioned. When the C1 to C4 alkylcarbonylamino group is substituted with a hydroxyl group or a carboxyl group, specific examples of the C1 to C4 alkylcarbonylamino group include, for example, hydroxyethylamino group and 2-hydroxypropionamidine. a hydroxy C1 to C4 alkylcarbonylamino group such as a hydroxy group or a 4-hydroxybutylideneamino group; a carboxy C1 to C4 alkylcarbonylamino group such as a 3-carboxypropylamino group; In the case where R8 to Rm in the formula (2) is jin-in the case of an alkylureido group, it is preferred to have a substituent as compared with the unsubstituted. In the case where the N'_C1 to C4 alkylureido group is substituted by a hydroxyl group, a sulfo group or a carboxyl group, 'as a specific example thereof, for example, N'-2-cartoethylglycan*, N'_3 N-hydroxyl-C1~C4 alkylurea group such as hydroxyethyl urea group; hydrazine, -2. sulfoethylureido group, hydrazine-3-sulfopropyl urea group, etc., sulfo group C1~ C4 alkylurea group; N-carboxyl group, N,_2-carboxyethylureido group, N,_3_carboxypropyl urea group, N'-4-carboxybutyl urea group, etc. N,-carboxyl group C1 to C4 alkylureido groups and the like. R to R10 in the formula (2) are a phenylamino group, a benzhydrylamino group or a phenylsulfonylamino group each having a substituent described in the following order, and the benzene contained in each group When the substituent of the ring is c丨~C4 alkyl, the alkyl group may be any of a straight chain, a bond, or a ring, and preferably 29 201005048 is a straight chain or a branched chain. Specific examples thereof include a straight chain such as a methyl group, an ethyl group, a n-propyl group or a n-butyl group; and a branched group such as an isopropyl group or an isobutyl group or a second butyl group. When r8 to RiQ in the formula (2) is an unsubstituted or benzene ring-substituted phenyl-amino group substituted by a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group or a carboxyl group, Specific examples thereof include unsubstituted phenylamino group or 2·oxyphenylamino group, 4-vaporylamino group, 2,4_digas «phenylamino group, and the like. An atom-substituted phenylamine group; a nonyl group substituted with a C1 to C4 alkyl group such as a nonylphenylamino group, a 4-nonylphenylamino group, a 4-secondbutylamino group Amino group; 2-nitrophenylamino group, nitro substituted phenylamino group such as 'nitrophenylamino group; 3-sulfophenylamino group, 4 sulfophenylamino group, 2, 4 a sulfo group-substituted phenylamino group such as a disulfophenylamino group or a 3,5-disulfophenylamino group; a 2-carboxyphenylamino group, a 4-carboxyphenylamino group, 2, 5 a carboxyamino group substituted with a carboxyl group such as a dicarboxyphenylamino group or a 3,5-dicarboxyphenylamino group. ® R to R1G in the formula (2) is an unsubstituted or phenyl ring via a gas atom, * an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group, or a carboxyl group substituted aramidylamino group. In the case of the case, as a specific example thereof, for example, an unsubstituted alkalylamino group, or a 2-gas benzoylamino group, a 4-chlorobenzhydryl group: a base, a 2,4-di group a benzylideneamino group substituted with a chlorine atom such as a chloroamino group, a 2-methylbenzoylamino group, a 3-mercaptoalkylamine group, a 4-mercaptobenzamide group a benzhydrylamino group substituted by a C1 to C4 alkyl group; a 2-nitrosomethylamino group, a 4-nitrobenzhydrylamino group, a 3,5-dinitrobenzimidylamine a benzhydrylamino group substituted by a cleavage group; a 2- benzoyl decylamino group 30 201005048 a sulfo group-substituted benzhydrylamino group such as a 4-sulfobenzylideneamino group; A carboxyl group-substituted benzhydrylamino group such as a carboxybenzylideneamino group, a 4-carboxybenzhydrylamino group or a 3,5-dicarboxybenzylideneamino group. When R8~ in the formula (2) is an unsubstituted or phenyl ring via a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group, or a carboxyl group substituted stupid base group Specific examples thereof include, for example, an unsubstituted phenylsulfonylamino group, or a 2-phenylphenylsulfonylamino group, and a 4-carbon group, which is substituted by a gas atom. Phenylsulfonylamino; 2-methylphenyl decylamino, 4-methylphenylsulfonylamino, 4-tert-butylphenylsulfonylamino, etc. via C1~ C4 alkyl-substituted phenylsulfonylamino group; 2-nitrophenylsulfonylamino group, 3-nitrophenylsulfonylamino group, 4-formylphenylsulfonylamino group, etc. a phenylsulfonylamino group substituted with a phenylsulfonylamino group; a phenylsulfonylamino group substituted by a sulfo group such as a 3-phenylsulfonylamino group; a 4-sulfophenylsulfonylamino group; A carboxysulfonylamino group such as a phenylsulfonylamino group or a 4-carboxyphenylsulfonylamino group or the like which is substituted by a carboxyl group. Specific examples of R8 to R10 in the formula (2) are preferably a hydrogen atom, a gas atom, a carboxyl group, a sulfo group, a methyl group, an ethyl group, a methoxy group, an ethoxy group or a 2-hydroxyethoxy group. , 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxyethylamine Base, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2,2'-dihydroxydiethylamino, 2,2' -Dicarboxydiethylamino, 3,3'-disulfodipropylamino, ethinylamino, 3-carboxypropylamino, 4-hydroxybutyrylamino, Ν'-carboxymethylureido , N'-2-sulfoethylureido, 4-sulfophenylamino, 2,4-disulfophenylamino, 2,5-dicarboxy 31 201005048 phenylamino group, stupid Mercaptoamine, 3-sulfobenzylideneamino, 2-carboxybenzylamino, phenylsulfonylamino, 4-mercaptosulfonylamino, 4-nitro Phenylsulfonylamino group, 3-sulfophenylsulfonylamino group, 4-carboxyphenylsulfonylamino group, etc., more preferably: hydrogen atom, gas atom, sulfo group, methyl group, methyl group , 2-carbylethoxy, 2-transylethoxy, 3-reperylpropoxy, 4-sulfobutoxy, dimethylamino, 3,3,disulfonyldipropylamine , Ethylamino, 3-mercaptopropylamino, ν,·μ-ethylureido, 2,4-dihydrophenylamino, benzhydrylamine, 4·methylbenzene The pyridylamino group is further preferably a hydrogenogen+, a hydroxy group, a methyl group, a methoxy group or a 3-hydroxypropoxy group. R8 to R1 in the formula (2). Preferably, the ruler 8 is a sulfopropylthio group or a 4-based T-thio group, preferably a mercaptopropylthio group or a 4-decylbutylthio group, more preferably a propylthio group; and R9 is hydrogen. Atom; R10 is a gas atom, a B-ylamino group, a methyl group or an ethyl group, a methoxy group or an ethoxy group, or a mercaptopropoxylate, preferably a gas atom, an ethylamino group, a methyl group V, Or a methoxy group, more preferably a gas atom β. A compound represented by the above formula (2) is preferably a compound of the above formula (4). In the formula (4), 'base A, r1. , and ... to Ri. The replacement of the j, including the ring shown by the dotted line, ^ fish clothing including the preferred one, etc., the above formula (2) can be the same. The compound of the above formula (4) is preferably a compound which is not represented by the above formula (5). In the formula (5), the radicals A, 辇# R to R ′ include the preferred ones, and may be the same as the above formula (4). R and R7 each independently represent a hydrogen atom 'chlorine atom; unsubstituted, or 32 201005048, a C1-C4 alkylcarbonylamino group substituted with a hydroxyl group or a carboxyl group; an unsubstituted C1 to C4 alkyl group, or Substituted, or C1 to C4 alkoxy substituted by a sulfo group or a hydroxyl group; R6 represents a hydrogen atom. R to R each independently represent a hydrogen atom; a chlorine atom; an unsubstituted, or a C1 to C4 alkylcarbonylamino group substituted with a hydroxyl group or a carboxyl group; a sulfo group ci~C4 alkoxy group; an unsubstituted C1 to C4 alkyl group ; unsubstituted, or a C1-C4 decyloxy group substituted by a thiol group; or a C1 to C4 alkylthio group substituted by a performance group or a thiol group; and R9 represents a hydrogen atom. In the formula (5), ... to R, 包括, including the preferred one, is equivalent to the equivalent of r8 & r1〇 in the above formula (1). The above formulas (2), (4), and (5) The basis of (6). In the above formula (4), n 独立 independently represents a group selected from the group consisting of: a hydrogen atom; a gas atom; a sulfo group; a nitro group; an amine gamma; an unsubstituted, or a (d), not Substituted c to C4 alkoxy, sulfo, or stilbyl substituted C1 to C4 alkoxy. 2 unsubstituted, or substituted by hydroxy, sulfo, or thiol ci~' 4 / group 醯base. .. _ $ in the formula (4) R " to C is unsubstituted or replaced by cn ~ (tetra) oxy, «, or _ substituted ci ~ \ oxy affair, the hospital oxy In the case of the best, the C1~C4 alkoxy groups in R5 and R7 are equivalent to each other. (2) R"H" in the formula... is m~CU based on the unsubstituted base group and the rim group. In the case of gamma == 33 201005048 Specific examples include, for example, mercaptosulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, and second a straight or branched unsubstituted C1~C4 alkylsulfonyl group such as butylsulfonyl, tert-butylsulfonyl, etc.; 2-hydroxyethylsulfonyl, 3-hydroxypropylsulfonyl Iso-hydroxy-C1~C4 alkylsulfonyl; 2-sulfopropylsulfonyl, 3-sulfopropylsulfonyl, 4-sulfobutylsulfonyl, etc. sulfo ci~C4 alkylsulfonate Carboxymethylsulfonate

參酿基、2-羧基乙基磺醯基、3_羧基丙基磺醯基等羧基C1〜 C4烷基磺醯基等。肀的R11至之具體例，較佳為：氫原子氣原子、磺基、硝基、甲氧基、乙氧基、2_羥基乙氧基 2-磺基乙氧基、3 _磺基丙氧基、4•磺基丁氧基、羧基甲氧基 2-羧基乙氧基、甲基磺醯基、乙基磺醯基、第三丁基磺基、2-羥基乙基磺醯基、3磺基丙基磺醯基、2羧基乙基酿基、笨基續酿基、4_氣苯基磺醯基、4-甲基苯基績酿基 2’4_二甲基苯基伽基、4_硝基苯基續醯基、4·續基苯其」酿基、2_缓基苯基續酿基、4-叛基苯基續酿基等’更佳土為佳ί原子、續基、確基、曱氧基、或甲基磺酿基 r進而氯原子、續基、f氧基、或3續基丙氧基較佳為至少1個為氫原子，且較佳為至w、個為氫原子料之取代基。較佳為至少式（6)中的Rii至 14 另兩個為氫原子、或者個為續基历佳為後者之組合。於-個為:磺基而另一個為氫原子’更時，進而^在、—為％基而另一個為氫原子之情來吟進而較佳為續基之取7于之障形代位置為萘并噻唑環之4位、e 34 201005048 位、8位之情形。更佳為將關於.上述式（1)及式（3)..之取代基所記載之較佳者彼此加以組合而形成之化合物，進而較佳為將更佳者彼此加以組合而形成之化合物。對進而較佳者彼此等亦相同。同樣地，更佳為將關於上述式（2)、（4)、（5)及式（6、之取代基所記載之較佳者彼此加以組合而形成之化合物，饔髻進而較佳為將更佳者彼此加以組合而形成之化合物。對進而較佳者彼此等亦相同。再者，如上所述，式（8)至（9)中，n、基A、Rl 至R10所取代之環，包括由虛線所示之上述式⑴中相同之含義。另外，就較佳者、較:= 之組合等而言’較佳的也是相同。色素（I)及（II)之鹽，為無機或有機陽離子之鹽。其中，作為無機鹽之具體例，可列舉驗金屬鹽、驗土金屬鹽、及錄鹽，較佳的無機鹽為鐘、納、却之鹽以及錄鹽。另外，作為有機陽離子之鹽，例如可列舉由下述式⑽ 所示之四離子，但並不i定於料。另外，亦可為游離酸、其互變異構物、以及其等之各種鹽之混合物。例如，可使用納鹽與録鹽之混合.物；游齙赌命.知m 游離酸輿鈉鹽之混合物，•鋰鹽、鈉鹽、以及銨鹽之混合物等你 & 等中的任一種組合。根據鹽之種類’亦有溶解性等物性值不m亦可藉由視需要而適當選擇鹽之種類，或者曰可么3有多種鹽等時 1 變化，來獲得具有符合目的之八的混合物。另外，色素 35 201005048 (I)與色素（II)不須為相同的鹽，可以分別是不同的鹽。 [化學式10] 干1 ζ4—n+—ζ2 Ζ3 (10) • 於式（10)中，Ζ1、Ζ2、Ζ3、Ζ4分別獨立表示選自由： , 氫原子、烷基、羥基烷基、以及羥基烷氧基烷基所組成之 10 群組中之基。作為式（10)中的ζ1、Ζ2、Ζ3、Ζ4之烷基的具體例，可列舉：曱基、乙基、正丙基、異丙基、正丁基、異丁基、第一丁基、第二丁基等。作為羥基烷基之具體例，可列舉：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。〜以烷奉。作為羥基烷氧基烷基之例，可列舉：羥基乙氧基曱基、2_羥基乙鲁氧基乙基、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，該等中較佳為羥基乙氧基 C1〜C4烷基。作為特佳者，可列舉：氩原子；甲基；羥基甲基、羥基乙基、3-羥基丙基、2-經基丙基、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乙氧基C1〜C4烷基。 36 201005048 式（10)之較佳化合物的z1、Z2、Z3、及Z4之組合之具體例示於下述表1中。 [表1] 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(OH)CH3 -CH2CH(OH)CH3 -CH2CH(OH)CH3 1-6 CH3 -CH2CH(OH)CH3 -CH2CH(OH)CH3 -CH2CH(OH)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(OH)CH3 CHS -CH2CH(OH)CH3A carboxyl group C1 to C4 alkylsulfonyl group such as a benzyl group, a 2-carboxyethylsulfonyl group or a 3-carboxypropylsulfonyl group. Specific examples of R11 to hydrazine are preferably: a hydrogen atom, a sulfo group, a nitro group, a methoxy group, an ethoxy group, a 2-hydroxyethoxy 2-sulfoethoxy group, and a 3-sulfopropyl group. Oxyl, 4 sulfobutoxy, carboxymethoxy 2-carboxyethoxy, methylsulfonyl, ethylsulfonyl, tert-butylsulfo, 2-hydroxyethylsulfonyl, 3 sulfopropylsulfonyl, 2 carboxyethyl, styrene, 4 phenyl sulfonyl, 4-methylphenyl 2'4 dimethyl phenyl , 4_nitrophenyl sulfhydryl, 4 · contigyl benzoic acid, 2 - hydroxyphenyl phenol, 4- thiophenyl phenol, etc. 'better soil is better ί atom And a hydrazine group, a decyl group, a decyloxy group, or a methyl sulfonyl group, and further preferably a chlorine atom, a contiguous group, an oxy group, or a 3 hydroxypropoxy group, at least one of which is a hydrogen atom, and is preferably To w, one is a substituent of a hydrogen atom. Preferably, at least the other two of Rii to 14 in the formula (6) are a hydrogen atom, or a combination of the latter and the latter. The one is: a sulfo group and the other is a hydrogen atom 'more time, and then ^, - is a % group and the other is a hydrogen atom, and then preferably a continuation basis It is the case of the 4 position of the naphthothiazole ring, the e 34 201005048 bit, and the 8 position. More preferably, the compound formed by combining the preferred substituents described in the above formula (1) and formula (3).. is further preferably a compound formed by combining more preferably with each other. . The same is true for each of the others. In the same manner, it is more preferred to combine the compounds described in the above formulas (2), (4), (5) and (6, and the preferred ones of the formula (6), preferably further More preferably, the compounds are formed by combining them with each other. Further preferably, they are the same as each other. Further, as described above, in the formulae (8) to (9), a ring substituted by n, a group A, and R1 to R10 is substituted. It includes the same meanings as in the above formula (1) indicated by a broken line. Further, it is preferably the same in comparison with a combination of: =, etc. The salts of the pigments (I) and (II) are inorganic. Or a salt of an organic cation. Specific examples of the inorganic salt include a metal salt, a soil-measuring metal salt, and a salt, and preferred inorganic salts are salts of bells, nanoparticles, and salts. The salt of the organic cation may, for example, be a tetraion represented by the following formula (10), but may not be a material. Further, it may be a mixture of a free acid, a tautomer thereof, and various salts thereof. For example, a mixture of sodium salt and salt can be used; a compound, a lithium salt, a sodium salt, and a mixture of ammonium salts, etc., any combination of you and the like. According to the type of the salt, there is also a property value such as solubility, and the salt may be appropriately selected as needed. The type, or the combination of a variety of salts, etc., to obtain a mixture having a purpose of 8. In addition, the pigment 35 201005048 (I) and the pigment (II) do not have to be the same salt, which may be different (1) In the formula (10), Ζ1, Ζ2, Ζ3, Ζ4 are independently selected from: , a hydrogen atom, an alkyl group, a hydroxyalkyl group, And a group of 10 groups consisting of a hydroxyalkoxyalkyl group. Specific examples of the alkyl group of ζ1, Ζ2, Ζ3, and Ζ4 in the formula (10) include a mercapto group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, isobutyl, first butyl, second butyl, etc. Specific examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, and 2 • Hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, etc., hydroxy group. Examples of the oxyalkyl group include a hydroxyethoxymethyl group, a 2-hydroxyethyl ethoxyethyl group, a 3-hydroxyethoxypropyl group, a 2-hydroxyethoxypropyl group, and a 4-hydroxy ethoxy group. A hydroxy C1 to C4 alkoxy C1 to C4 alkyl group such as a butyl group, a 3-hydroxyethoxybutyl group or a 2-hydroxyethoxybutyl group, and preferably a hydroxyethoxy group C1 to C4 alkyl group. As a particularly preferred one, there may be mentioned an argon atom; a methyl group; a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-propylpropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, and a 2-hydroxy group. Hydroxy C1~C4 alkyl group such as butyl; hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxy A hydroxyethoxy C1 to C4 alkyl group such as butyl, 3-hydroxyethoxybutyl or 2-hydroxyethoxybutyl. 36 201005048 A specific example of the combination of z1, Z2, Z3, and Z4 of the preferred compound of the formula (10) is shown in Table 1 below. [Table 1] 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(OH)CH3 -CH2CH(OH)CH3 -CH2CH(OH)CH3 1-6 CH3 -CH2CH(OH)CH3 -CH2CH(OH)CH3 -CH2CH(OH)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(OH)CH3 CHS -CH2CH(OH)CH3

上述式（1)所示之色素（I)的合成方法，係記載於專利文獻2。上述式（2)所示之三偶氮化合物例如可藉由如下所述之方法來合成。此外，為方便起見，各步驟中之化合物的酸性官能基以游離酸之形式表示。另外，下述式（11)至 (16)中，基A、R1至R10、及R5至R10所取代之分別的環，包括由虚線所示之環，均具有與上述式（2)中相同之含義。利用常法將由下述式（11 )所示之化合物加以二偶氮化，再利用常法使其與由下述式（12 )所示之化合物進行 37 201005048 偶合反應，獲得由下述式（13)所示之化合物。此外，式 (11)所示之化合物可依據東德專利第223149號說明書中所記載之方法來合成。另外，下述式（12)及（14)所示之化合物，可利用常法來合成。 [化學式11] NH2 (11) [化學式12] R8The method for synthesizing the dye (I) represented by the above formula (1) is described in Patent Document 2. The trisazo compound represented by the above formula (2) can be synthesized, for example, by the method described below. Further, for the sake of convenience, the acidic functional group of the compound in each step is represented by the form of a free acid. Further, in the following formulae (11) to (16), the respective rings substituted by the groups A, R1 to R10, and R5 to R10, including the ring indicated by a broken line, have the same as in the above formula (2) The same meaning. The compound represented by the following formula (11) is diazotized by a usual method, and then subjected to a coupling reaction with a compound represented by the following formula (12) by a conventional method: 37 201005048, and the following formula ( 13) The compound shown. Further, the compound represented by the formula (11) can be synthesized in accordance with the method described in the specification of the East German Patent No. 223149. Further, the compounds represented by the following formulas (12) and (14) can be synthesized by a usual method. [Chemical Formula 11] NH2 (11) [Chemical Formula 12] R8

NH2 (12) R10 [化學式13]NH2 (12) R10 [Chemical Formula 13]

R®R®

(13) )所示之化合物加以二述式（14)所示之化合 1 5 )所示之化合物。利用常法將所獲得之由式（13 偶氮化後’再利甩常法使其與由下物進行偶合反應，獲得由下述式（ [化學式14](13)) The compound shown is a compound represented by the compound (5) shown by the formula (14). The obtained formula (13 after nitriding) is further subjected to a coupling reaction with the substrate by a conventional method to obtain a formula (Chemical Formula 14).

(14) 38 (15) 201005048 [化學式15](14) 38 (15) 201005048 [Chemical Formula 15]

利用常法將所獲得之由式（15)所示之化合物加以二偶氮化後，再利用常法使其與由下述式（16)所示之化合物進行偶合反應，藉此可獲得由上述式（2)所示之三偶^ 化合物。 [化學式16]The obtained compound represented by the formula (15) is diazotized by a usual method, and then subjected to a coupling reaction with a compound represented by the following formula (16) by a usual method, whereby The trimeric compound represented by the above formula (2). [Chemical Formula 16]

(16) 此外’由上述式（16)所示之化合物可依據西德專利第2004488號說明書所記載之方法來合成。作為Ji述式（2)所示的本發明之化合物之較佳具體例’並無特別限定，可列舉由下述表2至表13中列舉之結構式所示之化合物等。於各表中，為方便起見，磺基、羧基等官能基係以游離酸之形式記載。 39 201005048(16) Further, the compound represented by the above formula (16) can be synthesized according to the method described in the specification of the West German Patent No. 2004488. The preferred embodiment of the compound of the present invention represented by the above formula (2) is not particularly limited, and examples thereof include compounds represented by the structural formulae shown in the following Tables 2 to 13. In the tables, functional groups such as a sulfo group and a carboxyl group are described in the form of a free acid for the sake of convenience. 39 201005048

[表2][Table 2]

201005048201005048

[表3][table 3]

41 20100504841 201005048

[表4][Table 4]

42 201005048 [表5]42 201005048 [Table 5]

化合物 No. 結構式 16 i〇jH AcHN 細 N「 SQ^I 17 fC^H SC^H SOjH S〇sH HjCd ACHM H° Λ SOaH 18 »0,$^ rJ0^ AcHM H3CO tVS)^ S〇aH 19 HO S. ^〇iH ^〇iH 3STl <>-/HsqipN SQ,H H3gd H3cd Hci^ <fS) SOjH 2 0 $〇3H s〇jH scyH Iosh H3d m H° rti 43 201005048Compound No. Structural Formula 16 i〇jH AcHN Fine N" SQ^I 17 fC^H SC^H SOjH S〇sH HjCd ACHM H° Λ SOaH 18 »0,$^ rJ0^ AcHM H3CO tVS)^ S〇aH 19 HO S. ^〇iH ^〇iH 3STl <>-/HsqipN SQ,H H3gd H3cd Hci^ <fS) SOjH 2 0 $〇3H s〇jH scyH Iosh H3d m H° rti 43 201005048

[表6][Table 6]

44 20100504844 201005048

[表7] 化合物 No. 結構式 2 6 $〇|H SC^H SOsH M〇aSrXc^ 手 SO^i Cf H3cf Hd 2 7 SC^H P°iH ITS e n3d Gr H°Q SOjH 2 8 S〇aM P°^H 2 9 SO3H so^i so3m IX e H ^\PH X/ > AC«T 8%« 30 SO^H SCbM SOaH _J_ j-ii 11· inf yWNWMHT l〇sH ^«HN CT S〇aH 45 201005048[Table 7] Compound No. Structural Formula 2 6 $〇|H SC^H SOsH M〇aSrXc^ Hand SO^i Cf H3cf Hd 2 7 SC^HP°iH ITS e n3d Gr H°Q SOjH 2 8 S〇aM P°^H 2 9 SO3H so^i so3m IX e H ^\PH X/ > AC«T 8%« 30 SO^H SCbM SOaH _J_ j-ii 11· inf yWNWMHT l〇sH ^«HN CT S〇 aH 45 201005048

[表8][Table 8]

46 201005048 [表9]46 201005048 [Table 9]

化合物 No ‘ 結構式 3 6 SOjH ^>8« 3 7 S〇iH J50^1 l〇3H ^ Η°ζ) H〇»® S0^4 3 8 JQjH S〇sH ϊ〇3η ^ Hcr^〇 3 9 5C%H SO^i P〇iH fS ^ p-^%CCC3NH2 W- Cl 4 0 f〇»H SOjH SOsH J〇L ^°^3V<PCWHZ W 尸^ c/ H^Q HOa® S〇3H 47 201005048Compound No 'Structure 3 6 SOjH ^>8« 3 7 S〇iH J50^1 l〇3H ^ Η°ζ) H〇»® S0^4 3 8 JQjH S〇sH ϊ〇3η ^ Hcr^〇3 9 5C%H SO^i P〇iH fS ^ p-^%CCC3NH2 W- Cl 4 0 f〇»H SOjH SOsH J〇L ^°^3V<PCWHZ W corpse ^ c/ H^Q HOa® S〇3H 47 201005048

粵 [表 ίο]Guangdong [table ίο]

48 20100504848 201005048

[表 11][Table 11]

49 20100504849 201005048

參 [表 12]Reference [Table 12]

50 20100504850 201005048

[表 13] 化合物 No. 結構式 5 6 XT S)^y ryj ^ςτ；Μ 5 7 SO3H SOsiH / Η,η HOjS 58 pC%M SQaH H〇^o3H s^>^r〇K sOaH HO^S 5 9 so3h so^h H〇SSSCCH / H〇^ ho3s 6 0 SOzH SG^H J SO3H HO3S 51 201005048 上述式（11)所示之化合物的二偶氣化公知之方法夾眘, 丹目：r 。實fe。例如，於硫酸、乙酸、或磷酸中，於例如-5〜2G°C、較佳為卜阶之溫缺卞又1定用亞硝醯硫酸來實施K (⑴所示之化合物之二偶氮化物與由式（⑴ 所不之化合物的偶合’亦於其自身公知之條件下實施。例如’於水或水性有機介質（水與水溶性有機溶劑之現合物等）中，於例如-5〜3(rc、較佳為1〇〜3η：之溫度實施。[Table 13] Compound No. Structural Formula 5 6 XT S)^y ryj ^ςτ;Μ 5 7 SO3H SOsiH / Η, η HOjS 58 pC%M SQaH H〇^o3H s^>^r〇K sOaH HO^ S 5 9 so3h so^h H〇SSSCCH / H〇^ ho3s 6 0 SOzH SG^HJ SO3H HO3S 51 201005048 A method known as disulfanation of a compound represented by the above formula (11) is cautious, Danmu: r. Real fe. For example, in sulfuric acid, acetic acid, or phosphoric acid, for example, a temperature of -5 to 2 G ° C, preferably a temperature-deficient temperature, and a nitrous acid sulfuric acid are used to carry out the K ((1) compound diazo) The compound and the coupling of the compound of the formula ((1) are also carried out under their own known conditions. For example, in water or an aqueous organic medium (a mixture of water and a water-soluble organic solvent, etc.), for example, -5 〜3 (rc, preferably 1〇~3η: temperature is implemented.

鲁由式（ιυ所示之化合物與由式（12)所示之化合物係使用約化學計量之用量。式（13)所示之化合物的二偶氮化，亦以其自身公知之方法來實施。於例如鹽酸、硫酸等無機酸之存在下，在水或水性有機介質中，於例如_5〜4(rc、較佳為5〜3〇。匸之溫度，使用亞石肖酸鹽來實施，例域甩亞硝酸納等亞確酸鹼金屬鹽。由< (13)所示之化合物之二偶氮化物與由式 Π4)所示之化合物的偶合，亦於其自身公知之條件下實施。例如，較有利的是於水或水性有機介質中，於例如_5 〜5〇°C、較佳為10〜3(TC之溫度，且於弱酸性至鹼性之？11 值進行。較佳為於弱酸性至弱鹸性之pH值，例如6〜ι〇之PH值實施。二偶氮化反應液為酸性，並且，由於偶合反應之進行而使得反應系統内進一步酸性化，因此較佳為藉由添加鹼來調整上述pH值。作為鹼，例如可使用：氫氧化鐘、虱氧化納等驗金屬虱乳化物；碳酸鐘、碳酸納、碳酸鉀等驗金屬碳酸鹽’·乙酸納等乙酸鹽；氨、有機胺等。由式（13)所示之化合物與由（14)所示之化合物係使用約 52 201005048 化學計量之用量。式（I5)所示之化合物的二偶氮化亦以其自身公知之方法來實施。於例如鹽酸、硫酸等無機酸之存在下，在水或水性有機介質（水與水溶性有機溶劑之混合物等广中，於例如-5〜40°C、較佳為10〜3〇。(：之溫度’使用亞硝酸鹽來實施’例如使用亞硝酸鈉等亞硝酸驗金屬鹽。由式（15 ) : 所示之化合物之二偶氮化物與由式（16)所示之化合物的 φ 偶合，亦於其自身公知之條件下實施。例如較有利的是在水或水性有機介質中，於例如_5〜5(rc、較佳為1〇〜3〇它之溫度，且於弱酸性至鹼性之pH值進行。較佳為於弱酸性至弱鹼性之pH值，例如6〜1〇之pH值實施，pH值之調整係藉由添加鹼來實施。作為驗，可使用與上述相同者。由式（15)所示之化合物與由（16)所示之化合物係使用約化學計量之用量。將由式（1)及（2)所示之一私叫厂"尚又鹽時，於偶合反應後，藉由將所需無機鹽或有機陽離子之鹽添於反應液中而進行鹽析，或者藉由添加鹽酸益而游離酸之形式進行單離，Μ ’’’、機酸而 V早離然後藉由視需要而使用水之水或水性有機介質#，對其進行清洗而除去於水性介質中利用所需無機或有機之驗加以中和^ 成所對應之鹽的溶液。此處所謂酸性之水，係心酸、鹽酸等無機酸或乙酸等有機酸溶解於水中而0 者。另外，所謂水性有機介質，係成為，之有機物質、可與水混合之所謂有機溶削寻’作為具體例 53 201005048 °列舉後述之本溶性有機溶劑等。作為無機鹽之例，可列舉氣化鐘、氣化納、氣化_等驗金屬鹽以及氯化銨、溴化録等銨鹽，作為有機陽離子之鹽之例’可列舉由上述式（10) 所不之有機胺的幽鹽等。作為無機驗之例，例如可列舉：氣氧化鐘、氳氧化鈉、氣氧化斜等驗金屬之氣氧化物氮、氧化銨，或者碳酸鋰、碳酸鈉、碳酸鉀等鹼金屬之碳酸鹽；等，作為有機鹼之例，可列舉有機胺，例如二乙醇胺、三 ❿ &醇胺等之由上述式（1〇)所示之四級錄類等，但並不限定於該等。對本發明之墨水組成物加以說明。含有色素（I)及（II) 之任者的本發明之墨水組成物，可對由纖維素形成之材料進行染色。另外’亦可對其他的具有碳醯胺鍵結之材料進行染色’可廣泛用於皮革、織物、紙之染色。 3有色素（I)及（II)的各反應液，可直接用於製造本發明之墨水組成物。亦即，藉由將分別另行合成而含有 . 肖色素之2種反應液加以混合，亦可製造本發明之墨水組 . 成物。但是，亦可首先使含有各色素之反應液個別乾燥，例如噴霧乾燥而將各色素單離；或藉由添加氯化鈉、氣化押、氯化鈣、硫酸鈉等無機鹽類而進行鹽析；或藉由添加鹽酸、硫酸、硝酸等無機酸來進行酸析；或者進行將上述鹽析與酸析加以組合而成的酸鹽析等，藉此單離各色素，將其混合來製備墨水組成物。本發明之墨水組成物’亦包含色素（〗）及（π)之2 種色素的任一者 '在滿足上述特定條件的範圍内，各色素 54 201005048 (I )及（II )可以分別是單獨的色素，也可以分別是多種色素的混合物。因此，本發明之墨水組成物，至少調配有 2種以上的色素。相對於墨水組成物之總質量，作為色素而含有於墨水組成物中之上述色素（n及（π)的總質量，通常為0.1〜20質量％、較佳為1〜1〇質量％、更佳為2〜8 質量％的比率，除此之外的墨水組成物中之其餘部分係以水作為主要介質。本發明之墨水組成物中，亦可進一步含有例如0〜3〇質量％之水溶性有機溶劑、例如〇〜1〇質量％之墨水製備劑，較佳為含有水溶性有機溶劑。另外，亦可視需要而基於調色等目的而於上述範圍内含有其他色素。此外作為墨水組成物之pH值，自使保存穩定性提高之方面考慮，較佳為PH值為5〜11，更佳為pH值為7〜1〇。另外，作為墨水組成物之表面張力，較佳為25〜7〇mN/m，更佳為乃 60 mN/m。進而，作為墨水組成物之黏度，較佳為3 〇爪以.The compound represented by the formula (I) and the compound represented by the formula (12) are used in a stoichiometric amount. The diazotization of the compound represented by the formula (13) is also carried out by a method known per se. In the presence of a mineral acid such as hydrochloric acid or sulfuric acid, in water or an aqueous organic medium, for example, _5 to 4 (rc, preferably 5 to 3 Torr. a sulfite metal salt such as sodium nitrite, a coupling of a diazo compound of the compound represented by <(13) and a compound represented by the formula )4), also under its own known conditions For example, it is advantageously carried out in water or an aqueous organic medium at a temperature of, for example, _5 to 5 ° C, preferably 10 to 3 (TC, and weakly acidic to basic). It is preferably carried out at a pH which is weakly acidic to weakly, for example, a pH of 6 to 〇. The diazotization reaction solution is acidic, and further acidification is caused in the reaction system due to the progress of the coupling reaction. Preferably, the above pH is adjusted by adding a base. As the base, for example, a hydrazine clock can be used.虱虱虱等等 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; The compound shown is a stoichiometric amount of about 52 201005048. The diazotization of the compound of the formula (I5) is also carried out by a method known per se. In the presence of a mineral acid such as hydrochloric acid or sulfuric acid, In water or an aqueous organic medium (a mixture of water and a water-soluble organic solvent, for example, -5 to 40 ° C, preferably 10 to 3 Torr. (: The temperature 'implemented using nitrite', for example, A metal salt of nitrous acid such as sodium nitrite. The coupling of the diazo compound of the compound of the formula (15): and the compound of the formula (16) is also carried out under its own known conditions. More preferably, it is carried out in water or an aqueous organic medium at a temperature of, for example, _5 to 5 (rc, preferably 1 Torr to 3 Torr, and at a pH of weakly acidic to basic. Preferably, it is weak. Acidic to weakly alkaline pH, for example, pH of 6~1〇, pH value The whole system is carried out by adding a base. As the test, the same as above can be used. The compound represented by the formula (15) and the compound represented by the formula (16) are used in an amount approximately stoichiometric. And (2) one of the privately-held factories "still salt", after the coupling reaction, salting out by adding a salt of a desired inorganic salt or organic cation to the reaction liquid, or by adding hydrochloric acid The form of the free acid is separated, the Μ ''', the acid is used, and the V is removed early, and then washed with water or an aqueous organic medium # as needed, and washed and removed in an aqueous medium. An inorganic or organic test is used to neutralize the solution of the corresponding salt. Here, the acidic water is a mineral acid such as cardio acid or hydrochloric acid or an organic acid such as acetic acid dissolved in water. In addition, the organic organic medium is an organic solvent and a so-called organic solvent which can be mixed with water. Specific examples 53 201005048 ° Hereinafter, the presently soluble organic solvent and the like are listed. Examples of the inorganic salt include a gasification clock, a gasification nano, a vaporization metal salt, and an ammonium salt such as ammonium chloride or bromine, and examples of the salt of the organic cation are exemplified by the above formula (10). ) The salt of organic amines, etc. Examples of the inorganic test include, for example, a gas oxide nitrogen such as a gas oxidation clock, sodium bismuth oxide, gas oxidation, or the like, and an alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate; Examples of the organic base include an organic amine such as a quaternary class represented by the above formula (1〇) such as diethanolamine, triterpene, and an alcoholamine, but are not limited thereto. The ink composition of the present invention will be described. The ink composition of the present invention containing any of the pigments (I) and (II) can dye a material formed of cellulose. In addition, it is also possible to dye other materials having a carbon amide bond, which can be widely used for dyeing leather, fabrics, and paper. 3 Each of the reaction liquids of the pigments (I) and (II) can be directly used for the production of the ink composition of the present invention. In other words, the ink set of the present invention can be produced by mixing two kinds of reaction liquids which are separately synthesized and contained. However, it is also possible to first dry the reaction liquid containing the respective pigments, for example, spray drying to separate the respective dyes, or to carry out the salt by adding inorganic salts such as sodium chloride, gasification, calcium chloride or sodium sulfate. Or acid precipitation by adding a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid; or acid precipitation by combining the above salting out and acid precipitation, thereby separating the respective pigments and mixing them to prepare Ink composition. The ink composition of the present invention also includes any of the two pigments of the pigments (?) and (π). Within the range satisfying the above specific conditions, each of the pigments 54 201005048 (I) and (II) may be separate The pigments may also be a mixture of a plurality of pigments, respectively. Therefore, at least two or more kinds of pigments are blended in the ink composition of the present invention. The total mass of the above-mentioned dyes (n and (π) contained in the ink composition as a coloring matter is usually 0.1 to 20% by mass, preferably 1 to 1% by mass, and more, based on the total mass of the ink composition. The ratio of 2 to 8 mass% is preferable, and the rest of the ink composition is water as a main medium. The ink composition of the present invention may further contain, for example, 0 to 3 % by mass of water-soluble. The organic solvent, for example, 墨水1% by mass of the ink preparation, preferably contains a water-soluble organic solvent. Further, other pigments may be contained in the above range depending on the purpose of coloring, etc., as needed. The pH value is preferably from pH 5 to 11, more preferably from pH 7 to 1 自 from the viewpoint of improving storage stability. Further, as the surface tension of the ink composition, it is preferably 25~ 7〇mN/m, more preferably 60 mN/m. Further, as the viscosity of the ink composition, it is preferably 3 〇 claws.

s以下，更佳為20 mPa.s以下。本發明之墨水組成物之pH 值、表面張力可利用如下所述之pH調整劑、界面活性劑來進行適當調整。在作為色素而含有於墨水組成物中之色素（〗）及（Η ) 的t質量申，各色素的比率較佳為介於色素（I )為1 〇〜3 〇質量％、色素（II)為70〜90質量％的範圍内，但對於色素（I)則更佳為15〜25質量％，對於色素（11)則更佳為 75 85質里％。基於調色等目的，亦可在不妨礙本發明之效果的範圍内’於本發明之墨水組成物中進而添加由上述 55 201005048 式（l)所不之色素（i)及由式（2)所示之色素（π)以外的其他色素。其他色素所能添加之量的範圍，由於添加該色素的目的等而不同，所以難以一概地決定。但作為大致的標準，在含有於墨水組成物中之色素的總質量中，色素（I )及（II )合計為70〜99質量％、其外的色素合計為 1〜30質量％左右即可。另外’如同上述，色素（I )及（H ) • 以外的其他色素亦可不添加於本發明之墨水組成物。 • 本發明之墨水組成物係將上述色素（I )及（II )視需要而與其他調色用等色素一起溶解於水或水溶性有機溶劑 (可與水混合之有機溶劑）中，並且視需要而添加有墨水製備劑者。根據將墨水組成物之黑色調整至無色調之中性Below s, more preferably 20 mPa.s or less. The pH value and surface tension of the ink composition of the present invention can be appropriately adjusted by using a pH adjuster or a surfactant as described below. In the t-mass of the pigments (〗〖) and (Η) contained in the ink composition as the coloring matter, the ratio of the respective dyes is preferably 1 〇 to 3 〇 mass% and the pigment (II) of the dye (I). It is in the range of 70 to 90% by mass, but more preferably 15 to 25% by mass for the pigment (I) and more preferably 75 to 85 % by mass for the pigment (11). For the purpose of toning or the like, the pigment (i) and the formula (2) which are not in the above formula (1) may be further added to the ink composition of the present invention within the range which does not impair the effects of the present invention. Other pigments other than the pigment (π) shown. The range in which the amount of other pigments can be added differs depending on the purpose of adding the dye, etc., and thus it is difficult to determine it in a comprehensive manner. However, as a general standard, the total amount of the dyes (I) and (II) in the total mass of the dye contained in the ink composition is 70 to 99% by mass, and the total amount of the other dyes is about 1 to 30% by mass. . Further, as described above, other pigments other than the pigments (I) and (H) may not be added to the ink composition of the present invention. In the ink composition of the present invention, the above-mentioned dyes (I) and (II) are dissolved in water or a water-soluble organic solvent (an organic solvent which can be mixed with water) together with other coloring matters, as needed, and If necessary, an ink preparation agent is added. Adjust the black color of the ink composition to a matte neutral

UeUtral)色調的目的等，可於本發明之墨水組成物中適當添加其他調色用色素等。於將該墨水組成物用作喷墨印表機用墨水之情形時’色素⑴及（Π)較佳為使用金屬冑離子之氣化物、硫酸鹽等無機雜質之含量少者。該無機暑㈣含量之標準大致為相對於色素總質量之t質量％以下 • %程度。製造無機雜質少的色素時，例如以利用逆渗透膜之通常方法，或者將色素之乾燥品或濕餅於甲醇等醇及水之混合溶劑中進行授拌，過渡分離析出物，加以乾燥等方法來進行脫鹽處理即可。，在上述墨水組成物之製備中，係基於下述目的而使帛以；整墨水之黏度、用以調整墨水之乾燥性、用以 t印刷後調整對記錄介質或記錄介質表面之墨水吸收層的、#為可使m之水溶性有機溶劑的具體例，例如可 56 201005048 丙二醇、1，2- 列舉f醇6醇、丙醇、異丙醇、丁醇、異丁醇、第二丁醇、第三丁醇等C1〜C4烧醇；Ν，Ν_二甲基甲醯胺、ν: -甲基乙醯fee等繞醜胺；2“比略烧_、Ν.甲基比钱嗣、經基乙基Κ錢_、Ν甲基。比㈣韻等内醯胺H 一曱基米坐啶2’、i 3二甲基六氫嘧啶_2酮等環式尿素類：丙酮、甲基乙基網、2_甲基_2,基戊烧_4·嗣等網或_ 醇’四氫呋喃、二噁燒等環狀醚；乙二醇、1，2-丙二醇、1>3· 醇、1，4-丁二醇、U6_己二醇二乙二醇三乙二醇、四乙二酸 __ 醇一丙一醇、聚乙二醇、聚丙二醇、硫二甘醇、二硫二甘w 甘醇等具有C2〜C6伸烷基單元之單、寡聚或聚燒二醇或硫謂；三經甲基丙燒、甘油、己劳 1，2’6 一醇等多謂（三醇乙二醇單甲鍵、乙二醇單乙醚、一乙二醇單曱醚、二乙二醇單乙醚、二乙二醇單丁· (丁基卡必醇）、=7 乙一醇早曱醚、三乙二醇單乙醚等多另麝醇1 C4烧基喊；r -丁内6旨、二甲基亞硬等。該等琴機溶劑可單獨㈣，亦可㈣兩㈣上。 — 在上述水各性有機溶劑中雖然亦包含三經甲邊 :烷：般在常溫為固體之物質，但該等即使是固體亦顯汚水合!生☆解於水時能夠基於與水溶性有機溶劑相同々二來使用’因此為方便起見，在本說明書中係作為記索於水溶性有機溶劑的範疇者。作4上述墨水組成物之製備中適宜使用之墨水製脊可列舉.防腐防黴劑、pH調整劑、螯合試劑、浪水办性紫外線吸收劑、水溶性高分子化合物 57 201005048 溶解劑、抗氧化劑、界面活性劑等。以下對該等試劑加以說明。作為防黴劑之具體例，可列舉：脫氫乙酸鈉（sodium dehydr〇acetate)、苯甲酸鈉、吡啶硫剩]-氧化物納、對羥基苯甲酸乙醋、U2-苯并異嗅蛛3_酮以及其鹽等。該等較佳為於墨水組成物中使用〇〇2〜1〇〇質量作為防腐劑之具體例，例如可列舉：有機硫系、有機氮硫系、有機南系、函代稀丙基颯系、碘代丙炔基系、Ν· •代烷硫基系、腈系、吡啶系、8.氧基喹啉系苯并噻唑系、異噻唾琳系、二硫醇系、氧化β比咬系、確基丙院系、有機錫系、盼系、四級銨鹽系、三嗪⑽犯―系噻嗪 (thiazine)系、苯胺系、金剛烷系二硫代胺基甲酸酿系、演節嗣系、溪乙酸_、無機鹽系等化合物。作為有機 _系化合物之具體例，例如可列 J 7 j列舉五氣苯酚鈉；作為氧化 •❿ 比咬系化合物之具體例，例如可' 』幻举2-«•比唆硫醇-i_氧化物納；作為異嘆㈣系化合物之具體例’例如可列舉：12. 苯并異㈣琳_3_酮、2_正辛基_4_異㈣琳_3__、5_氣1 甲基-4-異，唾琳_3_酮、5_氣_2_甲基_4_異噻終%嗣氣化鎂、5-氣_2•甲基_4_異嗟唾琳相氣化（、2_甲基|異售唑啉-3-酮氣化鈣等❶作為其 I. 、他的防腐防黴劑之具體例，可列舉：無水乙酸納、山梨酸鈉、笨甲酸鈉等。作為pH調整劑，若為可不 ^ 燮而脾黑卜對所製備之墨水造成不良影 a而將墨水之pH值控制在例如5〜々日用任意物質。作為其具體例 11 、’可使 J例如可列舉：二乙醇胺、三 58 201005048 乙醇胺、N_甲基二乙醇胺等院醇胺；氫氧化鋰、氫氧化納、氫氧化鉀等驗金屬之氫氧化物；氫氧驗（氨水）；碳酸裡、碳酸鈉、碳酸氫鈉、碳酸鉀等鹼金屬之碳酸鹽丨乙酸鉀等有機酸之驗金屬鹽1睃納、磷酸二鈉等無機驗等。作為螯合試劑之具體例，例如可列舉：乙二胺四乙酸鈉、次氮基三乙酸鈉、經基乙基乙二胺三乙酸納、二乙三胺五乙酸納、尿，咬二乙酸納等。瘳 :為防錢劑之具體例’例如可列舉:暖性亞硫酸鹽、 :代：酸納、硫代乙醇酸錢、亞確酸二異丙基錄、季戊四醇四硝酸酯、亞硝酸二環己基銨等。作為水溶性紫外線吸收劑之具體例，例如可列舉：經 =匕之二苯甲嗣系化合物、苯并三唾系化合物、水楊酸系化。物、肉桂酸系化合物、或三嗪系化合物。醇為水命14冋刀子化合物之具體例可列舉：聚乙烯纖維素衍生物、聚胺、聚亞胺等。胺作為色素溶解劑之具體例，例如可列舉：£己内酿碳酸乙二酯、尿素等。 ::抗氧化劑之具體例’例如可使用各種有機系以及金屬錯'物系防褪色劑。作為上述有機系防褪色劑之具體UeUtral) For the purpose of color tone, etc., other coloring matter for coloring or the like can be appropriately added to the ink composition of the present invention. When the ink composition is used as an ink for an ink jet printer, the pigments (1) and (Π) are preferably those having a small content of inorganic impurities such as a vapor of a metal ruthenium ion or a sulfate. The standard of the inorganic heat (four) content is approximately equal to or less than t% by mass of the total mass of the pigment. When a pigment having a small amount of inorganic impurities is produced, for example, a method in which a reverse osmosis membrane is used, or a dried product of a dye or a wet cake is mixed in a mixed solvent of an alcohol such as methanol or water, and the precipitate is separated and dried, and the like. To carry out desalination treatment. In the preparation of the above ink composition, the viscosity of the ink is adjusted, the drying property of the ink is adjusted, and the ink absorbing layer for adjusting the surface of the recording medium or the recording medium after t printing is used. And # is a specific example of the water-soluble organic solvent which can make m, for example, 56 201005048 propylene glycol, 1,2-exemplified f alcohol 6 alcohol, propanol, isopropanol, butanol, isobutanol, second butanol , C1~C4 octanol such as tert-butanol; Ν, Ν_dimethylformamide, ν:-methylacetamidinefee, etc.; 2" than slightly burned _, Ν. methyl than money 嗣经, 经 Ν 经经经经经经经经经经经经经经经经经经经经经经经经经经经经经四四四四四四、四四四四四、四、 a methyl ether network, a 2-methyl group, a ketone group, or a cyclic ether such as diol, tetrahydrofuran or dioxane; ethylene glycol, 1,2-propanediol, 1> , 1,4-butanediol, U6_hexanediol diethylene glycol triethylene glycol, tetraoxalic acid __ol monopropanol, polyethylene glycol, polypropylene glycol, thiodiglycol, disulfide a single C2~C6 alkyl unit such as diethylene w-glycol , oligomeric or polyalkylene glycol or sulfur; trimethoprim, glycerin, chlorhexidine 1,2'6-alcohol, etc. (triol glycol monomethyl bond, ethylene glycol monoethyl ether, one Ethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl (butyl carbitol), =7 ethyl alcohol early oxime ether, triethylene glycol monoethyl ether and other sterols 1 C4 Burning base shouting; r - Ding, 6 dimethyl, hard, etc. These phono solvents can be used alone (4) or (4) 2 (4) - In the above water organic solvents, it also contains three sides. : alkane: a substance that is solid at room temperature, but even if it is a solid, it is also effluent! ☆ When it is dissolved in water, it can be used based on the same as the water-soluble organic solvent. Therefore, for the sake of convenience, in this specification The medium is used as a category for water-soluble organic solvents. The ink ridge suitable for use in the preparation of the above ink composition can be exemplified by anti-corrosion and anti-fungal agents, pH adjusters, chelating agents, and water-based ultraviolet rays. Absorbent, water-soluble polymer compound 57 201005048 Solvent, antioxidant, surfactant, etc. Specific examples of the antifungal agent include sodium dehydrate acetate, sodium benzoate, pyridine sulfur remaining, sodium oxide, hydroxybenzoic acid, and U2-benzopyrene. 3_ketone, a salt thereof, etc. These are preferably a specific example of using a mass of 〇〇2 to 1 〇〇 in the ink composition as a preservative, and examples thereof include an organic sulfur system, an organic nitrogen sulfur system, and an organic south system. And the letter is a dipropyl fluorene system, an iodopropynyl group, a fluorenyl thiol system, a nitrile system, a pyridine system, an oxyquinoline benzothiazole system, an isothiazepine system, Thiol-based, oxidized beta-bite, acetylene, organotin, quaternary ammonium, triazine (10) thiazine, aniline, adamantane disulfide A compound such as a methionine, a sputum, a sulphuric acid, or an inorganic salt. Specific examples of the organic compound are, for example, a lithium pentoxide phenolate as listed in J 7 j; and a specific example of the oxidative oxime compound, for example, a singularity 2-«• 唆 thiol-i_ Oxide nano; as a specific example of the compound of the singular (four) system, for example, benzophenone (tetra) linyl -3- ketone, 2 - n-octyl _4 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 4-iso, salivin _3_ ketone, 5_gas_2_methyl_4_isothio end% 嗣 magnesia, 5-gas_2•methyl_4_isoindole saliva gasification ( Examples of the anti-corrosion and anti-mold agent of the 2-methyl-iso-oxazol-3-one-calcium oxide are as follows: anhydrous sodium acetate, sodium sorbate, sodium benzoate, etc. The pH adjuster may be used to control the pH of the ink by a spleen, and the pH of the ink may be controlled to, for example, 5 to 々. Any of the specific examples 11 and 'may be J, for example. For example, diethanolamine, three 58 201005048 ethanolamine, N-methyldiethanolamine and other hospital alcohol amines; lithium hydroxide, sodium hydroxide, potassium hydroxide and other metal hydroxides; hydrogen oxygen test (ammonia); Carbon An organic acid such as an alkali metal carbonate such as sodium, sodium hydrogencarbonate or potassium carbonate, or a metal salt such as potassium acetate or the like, may be an inorganic test such as sodium candihydrate or disodium phosphate. Specific examples of the chelating agent include, for example, Sodium amide, sodium nitrilotriacetate, sodium hexylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, urine, sodium diacetate, etc. 瘳: a specific example of an anti-money agent' For example, warm sulfite, : generation: acid sodium, thioglycolic acid, diacetyl acid, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, etc. as a water-soluble ultraviolet absorber Specific examples include, for example, a stilbene-based benzotriazine-based compound, a benzotris-based compound, a salicylic acid-based compound, a cinnamic acid-based compound, or a triazine-based compound. Specific examples of the knives compound include a polyvinyl cellulose derivative, a polyamine, a polyimine, etc. Specific examples of the amine as the dye dissolving agent include, for example, ethylene carbonate, urea, and the like. Specific examples of the antioxidants can be used, for example, various organic systems. And a metal-based anti-fading agent. As the specific anti-fading agent described above

ΠΓ:對苯二紛類、院氧基苯盼類、二烧氧基苯I 其“、本胺類、胺類、茚烷類、色滿(chroman)類、烷氧基本胺_、雜環類等。雜為界面活性劑之具體例，例如可列舉陰離子系、陽糸非離子系等公知之界面活性劑。 59 201005048 作為陰離子界面活性劑之具體例，可列舉炫基確酸鹽、烷基羧酸鹽、α·烯煙磺酸鹽、聚氧乙烯烷基醚乙酸鹽、 Ν-醯基胺基酸及其鹽、Ν_醯基甲基牛磺酸鹽、烷基硫酸鹽聚氡烷基醚硫酸鹽、烷基硫酸鹽聚氧乙烯烷基醚磷酸鹽、松香酸皂、蓖麻油硫酸酯鹽、月桂醇硫酸酯鹽、烷酚型磷 - 酸酯、烷基型磷酸酯、烷基芳基磺酸鹽、二乙基磺基琥珀 · 酸鹽、二乙基己基磺基琥珀酸鹽、二辛基磺基琥珀酸鹽等。 • 作為陽離子界面活性劑之具體例，可列舉2·乙烯基吡咬衍生物、聚4-乙烯基吡啶衍生物等。作為兩性界面活性劑之具體例，可列舉：月桂基二甲胺基乙酸甜菜驗、2_烧基·Ν-缓基甲基-Ν-經基乙基咪㈣鑌甜菜驗、椰子油脂肪酸酿胺丙基二甲胺基乙酸甜菜驗、聚辛基聚胺基乙基甘胺酸、或者Μ琳衍生物等。 ^為非離子界面活性劑之具體例，可列舉：聚氧乙婦 =基相、聚氧乙埽辛基苯鍵、聚氧乙埽十二烧基苯喊、 .聚氧乙烯油，'聚氧乙烯月㈣、聚氧乙埽貌基物系；聚氧乙婦油酸醋、臂宭7咕日聚氧乙烯二硬脂酸酯、山犁薛酕日钍私醋、山梨醇軒單酸山4醇酐月桂酸伴半、…㈣醇軒單油酸醋、山梨醇肝仏+油酸酯、聚氧乙烯耵 # -2 4 7 0 ® 酸酗、聚氧乙烯硬脂酸酯等酯糸，2,4,7,9-四曱基4 7 -枝 9 ...^ 炔 _4,7·一醇、3,6_二甲基·4-辛炔 3,6-一醇、3,5-二甲其_丨块 ΑΜ 土 -己炔-3-醇等乙块二醇（ · 作為其他的具體例醇）系， ”…可列舉：曰信化學公司製造的澈名 Surfynol 1 〇4、I 裊以的商姑、82、465、〇】fin STG 等。等墨水製備剩可單獨或混合使用。 201005048 本發明之墨水組成物係藉由將上述各成分以任意順序進行混合、攪拌而獲得。所獲得之墨水組成物可視需要以薄膜過濾器等進行過濾以除去雜物。另外，為了調整作為墨水組成物之黑色色調’除了上述色素（1)及（π)以外'"，亦可混合具有各種色調之其他色素。於此情形時，可將具有其他色調之黑色、或黃色、撥色、標色、獲紅、紅色、、洋紅色、紫色、藍色、藏青色、青色、綠色、其他顏色之色素加以混合來使用。本發明之墨水組成物可在各種領域中使用，適合用於書寫用水性墨水、水性印刷墨水、資訊記錄墨水等，特佳為用作喷墨用墨水’適合用於後述的本發明之噴墨印刷方法中。其次，對本發明之噴墨記錄方法加以說明。本發明之喷墨記錄方法的特徵在於使用上述本發明之墨水組成物來進行記錄。料發明之嘴墨記錄方法中，係使用含有上述墨水組成物之噴墨用墨水而於圖像接受材料（被記錄材料）上進行記錄，對此時所使用之墨水喷嘴等並無特別限制，可視目的來適當選擇^ 可採用公知之方法，例如：利用靜電吸引力使墨水喷出之電荷控制方式；利顧電元件之振動壓力的可控制喷印式沖〇P 〇n demand)方式（壓力脈衝方式）；將電信號轉變為聲波束而對墨水照射’利用其放射壓使墨喷波噴墨方式；對黑H $ 了墨水進行加熱而形成氣泡，利用所產生之壓力的熱喷墨’即氣泡噴墨（Bubble Jet，註冊商標）方式 61 201005048 等。亦包括··將稱為相片墨水量）低之墨水以小體積喷色調’使用墨水中之色素的方式；使用無色透明之再者’上述喷墨印刷方法中的在墨水中之色素濃度（色素含出多股之方式；以實質上相同之濃度不同的多種墨水來改良晝質墨水的方式等。 : 本發明之著色體’係經至少含有色素⑴* („)之 # *水組成物而被著色者’更佳為利用使用噴墨印表機之喷墨，己錄方法，藉由本發明之墨水組成物而被著色者。可被著色者並無特別限制，例如可列舉：紙、膜等資訊傳遞用片材；纖維或布（纖維素、尼龍、羊毛等）、皮革、彩色濾光片用基材等。其中，作為資訊傳遞用片材，較佳為經表面處理者，具體而言係於紙、合成紙、膜等基材上設置有墨水吸收層者。墨水吸收層可利用例如對上述基材浸泡或者塗佈陽離系聚σ物之方法’將多孔二氧化石夕氧化銘溶膠特殊究等可吸收墨水令之色素的多孔性白色無機物，與聚乙料或聚乙烯°比嘻㈣等親水性聚合物-起塗佈於上述基表面上之方法等來設置。設置有如此之墨水吸收層者通常被稱為喷墨專用、紙（膜）、光澤紙（膜）#。夕於上述資訊傳遞用片材中，特別是記錄於表面塗佈有夕孔性白色無機物之片材的圖像，已知會因臭氧氣體而使變色或褪色情況變得嚴重。然而，本發明之墨水組成物之耐臭氧氣體性優異’因此於對如此之被記綠材料進行喷墨 62 201005048 記錄時發揮特別大的效果。作為此種於表面上塗佈有多孔性白色無機物之片材之具體例’則可取得下述市售品：Canon(股）製造之商品名：ΠΓ: a mixture of benzodiazepines, alkoxybenzenes, and alkoxybenzenes I, "amines, amines, decanes, chromans, alkoxybenamines, heterocycles" Specific examples of the surfactant are, for example, a known surfactant such as an anionic or an anthraquinone nonionic surfactant. 59 201005048 Specific examples of the anionic surfactant include a leuco acid salt and an alkane. Carboxylic acid salt, α-alkenyl sulfonate, polyoxyethylene alkyl ether acetate, Ν-mercaptoamino acid and its salt, Ν-mercaptomethyl taurate, alkyl sulfate poly Alkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl sulfate, alkanol type phosphorus-ester, alkyl type phosphate, alkane a aryl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinate, etc. • Specific examples of the cationic surfactant include 2 a vinyl thief derivative, a poly-4-vinyl pyridine derivative, etc. As a specific example of the amphoteric surfactant, a : lauryl dimethylamino acetic acid beet test, 2_alkyl hydrazine, hydrazinyl methyl hydrazine, hydrazinyl amide (iv) 镔 beet test, coconut oil fatty acid, aminopropyl dimethyl amide acetic acid beet test, Polyoctyl polyaminoethylglycine, or ylide derivative, etc. ^ Specific examples of the nonionic surfactant include polyoxyethylene = base phase, polyoxyethyl octyl benzene bond, Polyoxyethylene oxime-based benzene scream, . Polyoxyethylene oil, 'polyoxyethylene month (four), polyoxyethylene enamel base system; polyoxyethylene oleic acid vinegar, arm 宭 7 咕 day polyoxyethylene two Stearic acid ester, mountain plough, 酕酕酕钍、山 sorbed sorbic acid, sorbitol Xuan acid mountain 4 alcoholic anhydride lauric acid with half, ... (4) Alcohol Xuan oil vinegar, sorbitol liver 仏 + oleate, polyoxyethylene 耵# -2 4 7 0 ® esters such as strontium sulphate and polyoxyethylene stearate, 2,4,7,9-tetradecyl 4 7-branched 9 ...^ alkyne _4,7-alcohol, Ethylene block diol such as 3,6-dimethyl-4-octyne 3,6-monool, 3,5-dimethyl dimethyl sulfonate-hexyne-3-ol (as another specific example) Alcohol), "... can be cited as the business name of Surfynol 1 〇 4, I 制造, manufactured by Yuxin Chemical Co., Ltd. 82,465, square, etc.] fin STG. The ink preparation can be used alone or in combination. 201005048 The ink composition of the present invention is obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition can be filtered by a membrane filter or the like as needed to remove foreign matter. Further, in order to adjust the black color tone as the ink composition, in addition to the above-mentioned dyes (1) and (π), other pigments having various color tones may be mixed. In this case, a mixture of black, or yellow, plucked, color, red, red, magenta, purple, blue, navy, cyan, green, and other colors having other hues may be mixed. use. The ink composition of the present invention can be used in various fields, and is suitable for use in aqueous writing inks, aqueous printing inks, information recording inks, and the like, and is particularly preferably used as an ink for inkjets' suitable for use in the inkjet of the present invention to be described later. In the printing method. Next, the ink jet recording method of the present invention will be described. The ink jet recording method of the present invention is characterized in that recording is carried out using the above-described ink composition of the present invention. In the ink jet recording method of the invention, the inkjet ink containing the ink composition is used for recording on an image receiving material (recording material), and the ink nozzle or the like used in this case is not particularly limited. Appropriate selection can be made according to the purpose. A well-known method can be used, for example, a charge control method for ejecting ink by electrostatic attraction; a controllable printing method for controlling the vibration pressure of the electric component (pressure) Pulse mode); converting an electrical signal into an acoustic beam to illuminate the ink 'using the radiation pressure to cause the ink jet to eject the ink method; heating the black H $ ink to form a bubble, using the generated pressure of the thermal inkjet' That is, Bubble Jet (registered trademark) method 61 201005048 and the like. Also included is a low-volume ink that is sprayed in a small volume to 'use a pigment in the ink; use a colorless transparent one'. The pigment concentration in the ink in the above inkjet printing method (pigment A method of improving a enamel ink by using a plurality of inks having substantially the same concentration: The color body of the present invention is a water composition containing at least a pigment (1)*(„) The colorant is more preferably colored by the ink jet using the ink jet printer, and the method of recording is carried out by the ink composition of the present invention. The colorant can be made without particular limitation, and examples thereof include paper and film. Such as a sheet for information transmission; a fiber or cloth (cellulose, nylon, wool, etc.), a substrate for leather, a color filter, etc. Among them, as a sheet for information transmission, it is preferably a surface-treated one, specifically The ink absorbing layer is provided on a substrate such as paper, synthetic paper, film, etc. The ink absorbing layer can be oxidized by using, for example, a method of immersing or coating a cation-free sigma substance on the substrate. Ming A porous white inorganic substance capable of absorbing an ink such as a pigment, and a hydrophilic polymer such as polyethylene or polyethylene (IV) is applied to the surface of the base, etc. The ink absorbing layer is generally referred to as inkjet-dedicated paper, film (film), and glossy paper (film) #. In the above-mentioned information-transferring sheet, in particular, a sheet coated with a fumatous white inorganic substance is printed on the surface. The image of the material is known to be discolored or discolored due to ozone gas. However, the ink composition of the present invention is excellent in ozone gas resistance. Therefore, inkjet 62 201005048 is recorded for such a green material. In particular, as a specific example of such a sheet coated with a porous white inorganic material on the surface, the following commercial product can be obtained: a product name manufactured by Canon:

Professional Photo Paper、Super Photo Paper、或 Mau ph〇t〇Professional Photo Paper, Super Photo Paper, or Mau ph〇t〇

Paper ; Seiko Epson(股）製造之商品名：相片用紙（光澤）、 PM Matt 紙、Crispia ;日本 Hewlett-Packard (股）製造之商品名：Advance Photo用紙；Fuji Film (股）製造之畫彩相片加工Pro等。利用本發明之喷墨記錄方法於普通紙或上述資訊傳遞用片材等被記錄材料上進行記錄時，例如若將含有上述墨水組成物之容器裝填在喷墨印表機之特定位置，利用通常之方法在被記錄材料上進行記錄即可。本發明之噴墨印刷方法亦可將本發明之黑色墨水組成物，與例如公知之洋紅色、青色、黃色、以及視需要之綠色、藍色（或紫色）以及紅色（或橙色）等各色墨水組成 -Φ 物’作為墨水組而併用。 . 各色墨水組成物係被注入至各個容器中，將該各容器與含有本發明之黑色墨水組成物之容器同樣地裝填在喷墨印表機之特定位置而用於喷墨記錄。本發明之墨水組成物即使長期保存亦不會產生結晶析出、物性變化、色調變北等，因此儲藏穩定性良好。另外，本發明之墨水組成物可用於喷墨記錄、書寫用具。. . . ' .... 進而’於記錄在資訊記錄用片材、特別是喷墨專用紙 63 201005048 上之it形時，其記錄圖像之列印濃度高，並且記錄圖像之各種耐久性，亦即耐水性、耐光性、耐氧化性氣體性、耐濕性等’且特別是耐臭氧氣體性以及耐光性優異。 [實施例] 以下’利用實施例來對本發明進行更具體之說明，但本發明不受以下實施例之任何限定。Paper; Seiko Epson (share) trade name: photo paper (gloss), PM Matt paper, Crispia; Japan Hewlett-Packard (share) trade name: Advance Photo paper; Fuji Film (stock) made of color photos Processing Pro and so on. When the inkjet recording method of the present invention is used for recording on a recording material such as plain paper or the above-described information transfer sheet, for example, when a container containing the ink composition is loaded at a specific position of an inkjet printer, The method can be recorded on the material to be recorded. The ink jet printing method of the present invention can also be used for the black ink composition of the present invention, and various inks such as magenta, cyan, yellow, and, if desired, green, blue (or purple), and red (or orange). The composition -Φ object' is used as an ink set. The ink compositions of the respective colors are injected into the respective containers, and the containers are loaded in a specific position of the ink jet printer for ink jet recording in the same manner as the container containing the black ink composition of the present invention. The ink composition of the present invention does not cause crystal precipitation, physical property change, and color tone to be changed even after long-term storage, and therefore the storage stability is good. Further, the ink composition of the present invention can be used for ink jet recording and writing. . . . '.. Further, when recording on the information recording sheet, especially the ink shape on the inkjet paper 63 201005048, the recording density of the recorded image is high, and the various durability of the recorded image is recorded. The properties, that is, water resistance, light resistance, oxidation resistance, moisture resistance, and the like, are particularly excellent in ozone gas resistance and light resistance. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the following examples.

I _ 本文中只要無特別說明，則「份」及「％」為質量基準。另外，於下述各式中，為方便起見，磺基、羧基等官能基係以游離酸之形式表示。另外，以下所記載之1)11值以及反應溫度，均表示反應系統内之測定值。另外，所合成之化合物的最大吸收波長（λ max)係於 PH值為7〜8的水溶液中且3〇〇 nm至8〇〇的範圍内測疋’在實施例中記載所測定之化合物的測定值。 ❷ $外’氣化鈉及硫酸鈉，也就是無機雜質，分別使用離子層析法來測定氣化物離子及硫酸離子的含量，各離子的對應陽離子（counter cati〇n)全部換算為納離子來計算。再者，實施例所合成的各色素，均對水表現出100 g/L 以上之溶解度。 [合成例1 ] (步驟1) 將17.1伤之4-氯—3-硝基甲苯、；22.0份之3_疏基丙烷磺酸鈉、及60份之二甲基亞砜的混合物，於攪拌下加熱至 64 201005048 60°C，此時添加11.2份之碳酸鈉。添加後，加熱至12〇〜 130 C，並於同溫度下攪拌6小時。將反應液冷卻至室溫後，添加至330份之2-丙醇。將所析出之固體過濾分離，並以100份之2-丙醇來清洗。將所得之固體添加至3〇〇份之水中後，以35〇/。之鹽酸來使pH值為7 〇〜7 5，藉由添加氣化鈉來進行鹽析，並將析出物過濾分離，而獲得含有下述式（17)所示之化合物的濕餅。 [化學式17]I _ Unless otherwise stated, “parts” and “%” are the quality standards. Further, in the following formulas, for the sake of convenience, a functional group such as a sulfo group or a carboxyl group is represented by a free acid. Further, the values of 1) and the reaction temperatures described below indicate the measured values in the reaction system. Further, the maximum absorption wavelength (λ max) of the synthesized compound is in an aqueous solution having a pH of 7 to 8 and is measured in the range of 3 〇〇 nm to 8 疋 in the examples. measured value. ❷ $External 'gasification of sodium and sodium sulfate, that is, inorganic impurities, respectively, using ion chromatography to determine the content of vapor ions and sulfate ions, the corresponding cations of each ion (counter cati〇n) are all converted to nano ions Calculation. Further, each of the dyes synthesized in the examples exhibited a solubility of 100 g/L or more with respect to water. [Synthesis Example 1] (Step 1) A mixture of 17.1 killed 4-chloro-3-nitrotoluene, 22.0 parts of sodium 3-sulfopropane sulfonate, and 60 parts of dimethyl sulfoxide was stirred. Heat down to 64 201005048 60 ° C, at this time add 11.2 parts of sodium carbonate. After the addition, it was heated to 12 Torr to 130 C and stirred at the same temperature for 6 hours. After the reaction solution was cooled to room temperature, it was added to 330 parts of 2-propanol. The precipitated solid was separated by filtration and washed with 100 parts of 2-propanol. The obtained solid was added to 3 parts of water to give 35 Å/. Hydrochloric acid was used to bring the pH to 7 〇 to 7 5, salting out by adding sodium gasification, and the precipitate was separated by filtration to obtain a wet cake containing the compound represented by the following formula (17). [Chemical Formula 17]

(步驟2) 於120份之水中，加入16 6份之鐵粉及3」份之35% 鹽酸’並加熱至9CTC。40分鐘後，於此溶液中，以約15 分鐘滴加將上述（步驟1)所獲得之濕餅懸浮於60份之水參中而得者。滴加後，將反應液以85〜90°C攪拌2小時，再 . 冷卻至室溫。濾除不溶物之後，於濾液中添加35%鹽酸，並將藉由酸析而析出之固體過濾分離，乾燥後獲得16·7份之下述式（18)所示之化合物。 [化學式18](Step 2) In 16 parts of water, 16 6 parts of iron powder and 3 parts of 35% hydrochloric acid' were added and heated to 9 CTC. After 40 minutes, the wet cake obtained in the above (Step 1) was suspended in 60 parts of water ginseng in about 15 minutes in this solution. After the dropwise addition, the reaction solution was stirred at 85 to 90 ° C for 2 hours, and further cooled to room temperature. After the insoluble matter was filtered off, 35% hydrochloric acid was added to the filtrate, and the solid precipitated by acid precipitation was separated by filtration, and dried to give 16.7 parts of the compound of the formula (18) below. [Chemical Formula 18]

(步驟3) 65 201005048 將29.2份之硫氰酸鉀溶解於26〇份之甲醇，接著加入 26伤之硫酸30.4份之2_萘_5,7二績酸。於所獲得之溶液中滴加34份之35%過氧化氫水，於55〜6〇β(：攪拌丄小時。冷卻至20°C後添加7G份之㈣氨水，將析出固體過慮分離，藉此獲得28.8份的由下述式（19)所示之化合物。 [化學式19](Step 3) 65 201005048 29.2 parts of potassium thiocyanate was dissolved in 26 parts of methanol, followed by the addition of 26 parts of sulfuric acid 30.4 parts of 2_naphthalene_5,7. Add 34 parts of 35% hydrogen peroxide water to the obtained solution at 55~6〇β (: stirring for 丄 hours. After cooling to 20 °C, add 7G parts of (4) ammonia water to separate the precipitated solids. This gave 28.8 parts of a compound represented by the following formula (19). [Chemical Formula 19]

(步驟4) 將18伤的由上述式（19)所示之化合物於〜緩緩添加至180份的30%發煙硫酸中後，升溫至16〇<>c，於相同温度中攪拌1小時。將反應液以約1 5分鐘滴加至 158份之冰水中，獲得含有由下述式（2〇)所示之化合物的溶液。於該溶液中添加6.3份之60%硝酸，於5〜1(rc以約1〇分鐘滴加25份之40%亞硝醯硫酸，使其反應1小時，藉此獲得二偶氮反應液。於2〇〇份之水中添加13.1份的由上述式（18)所示之化合物、7.0份之胺基磺酸’繼而添加氫氧化鈉以使pH值為5.〇〜5.5，藉此獲得水溶液。於20〜30°C之反應溫度以約20分鐘向所獲得之水溶液中滴加上述二偶氮反應液。於滴加結束後，於相同溫度中攪拌1小時，添加8〇〇 66 201005048 份之丙酮後，.過濾分離析出固體，藉此獲得含有由下述式 (2 1 )所示之化合物的濕餅。 [化學式20](Step 4) 18 compounds of the compound represented by the above formula (19) were gradually added to 180 parts of 30% fuming sulfuric acid, and then heated to 16 〇 <>c, and stirred at the same temperature. 1 hour. The reaction solution was added dropwise to 158 parts of ice water over about 15 minutes to obtain a solution containing a compound represented by the following formula (2). To the solution, 6.3 parts of 60% nitric acid was added, and 25 parts of 40% of nitrosylsulfuric acid was added dropwise at about 1 minute for about 1 minute, and the reaction was carried out for 1 hour, whereby a diazo reaction liquid was obtained. Adding 13.1 parts of the compound represented by the above formula (18) and 7.0 parts of the aminosulfonic acid ' to 2 parts of water, followed by adding sodium hydroxide to have a pH of 5. 〇 to 5.5, thereby obtaining an aqueous solution The above diazo reaction solution was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C for about 20 minutes. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, and 8 〇〇 66 201005048 parts were added. After the acetone, the solid is separated by filtration, whereby a wet cake containing a compound represented by the following formula (2 1 ) is obtained.

[化學式21][Chemical Formula 21]

(步驟5) 於110份之水中加入上述（步驟4)所獲得之濕餅，繼而加入氫氧化鈉以使pH值為7.0〜7.5，藉此獲得水溶液。於所得之水溶液中滴加4.6份之35%鹽酸，繼而於15 〜20°C之反應溫度中以約5分鐘滴加4.6份之40%亞硝酸鈉水溶液，使其反應1小時，藉此獲得二偶氮反應液。另一方面’於35份之水中添加5.4份之下述式（22) 所示之化合物’繼而添加氫氧化鈉以使pH值為5.0〜5.5 , 藉此獲得水溶液。於20〜30°C之反應溫度中以約20分鐘向此水溶液中滴加如上述般所獲得之二偶氮反應液。其間’於反應系統内添加碳酸鈉，使pH值保持為5.0〜5.4。於滴加結束後’於相同溫度中攪拌2小時，添加氯化鈉來進行鹽析’過濾分離已析出之固體，藉此獲得含有下 67 201005048 述式（ 23)所示之化合物的濕餅。再者，由下述式利特開 2004-083492 [化學式22] (22)所示之化合物，係利用日號公報中所記載之方法獲得。本專(Step 5) The wet cake obtained in the above (Step 4) was added to 110 parts of water, and then sodium hydroxide was added to bring the pH to 7.0 to 7.5, whereby an aqueous solution was obtained. To the obtained aqueous solution, 4.6 parts of 35% hydrochloric acid was added dropwise, and then 4.6 parts of a 40% aqueous solution of sodium nitrite was added dropwise at a reaction temperature of 15 to 20 ° C for about 5 minutes to cause a reaction for 1 hour. Diazo reaction solution. On the other hand, 5.4 parts of the compound represented by the following formula (22) was added to 35 parts of water, followed by addition of sodium hydroxide to have a pH of 5.0 to 5.5, whereby an aqueous solution was obtained. The diazo reaction solution obtained as described above was added dropwise to the aqueous solution at a reaction temperature of 20 to 30 ° C for about 20 minutes. In the meantime, sodium carbonate was added to the reaction system to maintain the pH at 5.0 to 5.4. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and sodium chloride was added to carry out salting out. The precipitated solid was separated by filtration, whereby a wet cake containing the compound of the formula (23) of the following 67 201005048 was obtained. Further, the compound represented by the following formula is disclosed in the method described in the Japanese Patent Publication No. 2004-083492 [Chemical Formula 22] (22). This special

(22)(twenty two)

[化學式23][Chemical Formula 23]

(23) (步驟6) 將上述（步驟5 )中所獲得·的含有由式（23 )所示化合物的濕餅溶解於15〇份之7"，滴加5 〇份之35: 酸繼而於20〜25C之反應溫度以約5分鐘滴加18份 40%亞硝酸鈉水溶液，使其反應1小時，藉此獲得二偶反應液。另方面，於55份之水中添加2·4份之由國際公開 2007/07793 1號小冊子所述方法而獲得之式（24 )所示之化合物，繼而添加氫氧化鈉以使pH值為7.5〜8.0，而獲得水溶液。於20〜3(TC之反應溫度中以約3〇分鐘向此水溶液中滴加如上述般所獲得之二偶氮反應液。其間，於反應系統内添加碳酸鈉’使pH值保持為7 〇〜8 〇。 68 201005048 於滴加結束後，於相同溫度中攪拌2小時，添加氣化鈉來進行鹽析，過濾分離已析出之固體，藉此獲得濕餅。將所獲得之補溶解於16G份之水中，添加㈣份之丙嗣後’過濾分離已析出之固體’藉此獲得濕餅。將所獲得之濕餅再次溶解於110份之水中， τ 添加280份之丙酮後，過慮分離已析出之固體’加以乾燥，藉此獲# 7.2份的本發明之由下达式（25)所示之化合物（表2中的紹之化合物）來作為鈉鹽。此化合物相杂初相田於本發明之墨水組成物中所使用的色素（Π )。 λ max : 585 nm。 [化學式24](23) (Step 6) The wet cake containing the compound represented by the formula (23) obtained in the above (Step 5) is dissolved in 15 parts of 5", and 5 parts of 35 parts are added dropwise: the acid is then The reaction temperature of 20 to 25 C was dropwise added to 18 parts of a 40% aqueous solution of sodium nitrite for about 5 minutes, and the mixture was allowed to react for 1 hour, whereby a di-coupled reaction liquid was obtained. On the other hand, 2 to 4 parts of the compound of the formula (24) obtained by the method described in the pamphlet of International Publication No. 2007/07793 No. 1 was added to 55 parts of water, followed by addition of sodium hydroxide to bring the pH to 7.5~ 8.0, while obtaining an aqueous solution. The diazo reaction solution obtained as described above was added dropwise to the aqueous solution at a reaction temperature of TC of 20 to 3 at about 3 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH at 7 〇. ~8 〇. 68 201005048 After the completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, sodium sulfate was added for salting out, and the precipitated solid was separated by filtration to obtain a wet cake. The obtained residue was dissolved in 16G. In the water, after adding (four) parts of propylene, 'filtering and separating the precipitated solids' to obtain a wet cake. The obtained wet cake is redissolved in 110 parts of water, and τ is added with 280 parts of acetone, and the separation has been precipitated. The solid was dried to obtain #7.2 parts of the compound of the present invention (the compound shown in Table 2) of the present invention as a sodium salt. This compound is mixed with the first phase in the present invention. Pigment (Π) used in the ink composition. λ max : 585 nm [Chemical Formula 24]

h3Q PNh3Q PN

(24) [化學式25](24) [Chemical Formula 25]

(25) ο [合成例2] (步驟1 ) 氯硝基苯、22.0份之3_巯基丙烷添加19·2份之2,5- 69 201005048 磺酸鈉、及60份之二甲基亞颯，於攪拌下，加熱至6(rc，並添加11.2份之碳酸鈉。於添加後加熱至120〜13〇，並於相同溫度中攪拌6小時。將反應液冷卻至室溫後，一面攪拌一面添加至330份之2_丙酵中。過濾分離已析出之固體’並以100份之2-丙醇來清洗固體β將所得之固體添加至300份之水中後’以35%鹽酸使pH值為7 〇〜7 5，藉由添加氣化鈉來進行鹽析，將析出物過濾分離，而得到含有 • 下述式（26 )所示之化合物的濕餅。繼而，對含有式（26 ) 所示之化合物的濕餅添加17〇份之水、丨8份之活性碳、〇4 份之無水三氣化鐵，於挽拌下，於70。(：〜8(TC以約30分鐘滴加15份之8〇%肼一水合物。滴加後於85〜95<>c攪拌3小時，冷部至室溫。濾除不溶物後，添加50°/。硫酸並酸析藉此過濾分離所獲得之析出物，而獲得含有下述式 (27 )所示之化合物的濕餅。 [化學式26](25) ο [Synthesis Example 2] (Step 1) Chloronitrobenzene, 22.0 parts of 3_mercaptopropane, 29.2 parts of 2,5-69 201005048 sodium sulfonate, and 60 parts of dimethyl sulfoxide After stirring, heat to 6 (rc, and add 11.2 parts of sodium carbonate. After the addition, heat to 120~13 Torr, and stir at the same temperature for 6 hours. After cooling the reaction solution to room temperature, stir while stirring. Add to 330 parts of 2_propy yeast. Separate the precipitated solid by filtration and wash the solid with 100 parts of 2-propanol. Add the obtained solid to 300 parts of water and then adjust the pH with 35% hydrochloric acid. 7 〇 to 7 5, salting out by adding sodium carbonate, and separating the precipitates to obtain a wet cake containing the compound represented by the following formula (26). Then, the formula (26) is contained. The wet cake of the compound shown was added with 17 parts water, 8 parts of activated carbon, 4 parts of anhydrous iron trioxide, and mixed with water at 70. (: ~8 (TC drops in about 30 minutes) Add 15 parts of 8% hydrazine monohydrate. After adding dropwise, stir at 85~95 <>c for 3 hours, cool to room temperature. After filtering off the insolubles, add 50 ° / sulfuric acid and acid precipitation The obtained was separated by filtration of the precipitate, to obtain a wet cake containing a compound of the following formula (27) shown in the [Chemical Formula 26]

[化學式27][Chemical Formula 27]

(步驟2 ) 70 201005048 除了使用含有合成例2之（步驟1 )中所獲得的式（27 ) 所示之化合物的濕餅來代替合成例1之（步驟4 )中的13.1 份之由式（18)所示之化合物以外，以與實施例i相同之方式，獲得3.4份之由下述式（28)所示之化合物（表7 中的No.26之化合物）來作為鈉鹽。此化合物相當於本發明之墨水組成物中所使用的色素（π )。 λ max ： 595 nm 〇 [化學式28](Step 2) 70 201005048 In place of the wet cake of the compound represented by the formula (27) obtained in the (Step 1) of Synthesis Example 2, instead of the formula (13.1 parts) of (Step 4) of Synthesis Example 1 ( In the same manner as in Example i, 3.4 parts of a compound represented by the following formula (28) (a compound of No. 26 in Table 7) was obtained as a sodium salt. This compound corresponds to the pigment (π) used in the ink composition of the present invention. λ max : 595 nm 〇 [Chemical Formula 28]

[合成例3] 以專利文獻2之實施例丨所記載的方法，來獲得i 3〇 ® 伤之由上述式（7 )所示之色素來作為本發明之墨水組成物中所使用的色素（I)。 [(A)墨水之製備] [實施例1] 藉由將下述表14中所中所記載之各成分加以混合而製備[Synthesis Example 3] The dye represented by the above formula (7) was obtained as the dye used in the ink composition of the present invention by the method described in Example 专利 of Patent Document 2 ( I). [(A) Preparation of Ink] [Example 1] Prepared by mixing the components described in Table 14 below

71 201005048 而使總量成為1 〇〇·〇份。所獲得之墨水在儲藏中並且即使在長期保存後，亦不會產生沈澱分離、不會產生物性變化。 [表 14] 合成例1中所獲得之色素：色素（II) 4.0份合成例3中所獲得之色素：色素（I) 1.0份甘油 5.0份尿素 5.0份 N-曱基-2-吡咯烷酮 4.0份異丙醇 3.0份丁基卡必醇 2.0份 ‘界面活性劑 0.1份 _ (商品名Surfynol 104，曰信化學公司製造） φ 水+氫氧化鈉 75.9份共計 100.0份 [實施例2] 藉由將下述表15中所記載之各成分加以混合而製備本發明之墨水組成物後，利用0.45 // m之薄膜過濾器來過濾，藉此獲得喷墨用之墨水。將此墨水之製備作為實施例 2。另外，水係使用離子交換水。再者，墨水組成物之pH •φ 值係利用1.0%之氫氧化鈉而調整為pH =8〜10，並添加水 . 而使總量成為1 〇〇.〇份。所獲得之墨水在儲藏中並且即使 • 在長期保存後，亦不會產生沈澱分離、不會產生物性變化。 [表 15] 合成例2中所獲得之色素：色素（II) 4.0份合成例3中所獲得之色素：色素（I) 1.0份甘油 5.0份尿素 5.0份 N-甲基-2-吡咯烷酮 4.0份異丙醇 3.0份丁基卡必醇 2.0份界面活性劑 0.1份 (商品名Surfynol 1〇4，曰信化學公司製造） 72 201005048 水+氫氧化鈉 75.9份共計 100.0份 [比較例1〜3] 分別單獨使用色素（I)及（II)來作為比較對象之墨水，且藉由混合下述表16、17、18所述之各成分來製備墨水組成物，並利用0.45 之薄膜過濾器來過濾，藉此獲得喷墨用之比較用墨水。水係與實施例1同樣使用離子交換水《再者，墨水組成物之pH值係利用1 .〇%之氫氧化納水溶液而調整為pH = 8〜10，並添加水而使總量成為1 〇〇份。僅使用合成例1中所獲得之色素（II )來作為色素的墨水之製備係作為比較例1，僅使用合成例2中所獲得之色素（Π)的墨水之製備係作為比較例2，僅使用合成例3 中所獲得之色素（I )的墨水之製備係作為比較例3。71 201005048 And the total amount becomes 1 〇〇·〇. The obtained ink is in storage and does not cause precipitation separation or physical property change even after long-term storage. [Table 14] Pigment obtained in Synthesis Example 1: Pigment (II) 4.0 parts Pigment obtained in Synthesis Example 3: Pigment (I) 1.0 part glycerin 5.0 parts urea 5.0 parts N-mercapto-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts butyl carbitol 2.0 parts 'activator 0.1 parts _ (trade name Surfynol 104, manufactured by Yuxin Chemical Co., Ltd.) φ water + sodium hydroxide 75.9 parts total 100.0 parts [Example 2] The ink compositions of the present invention were prepared by mixing the components described in the following Table 15, and then filtered using a 0.45 //m membrane filter to obtain an ink for inkjet. The preparation of this ink was taken as Example 2. In addition, ion-exchanged water is used for the water system. Further, the pH of the ink composition was adjusted to pH = 8 to 10 by using 1.0% sodium hydroxide, and water was added thereto to make the total amount 1 〇〇. The obtained ink is stored and even if it is stored for a long period of time, precipitation separation does not occur and physical properties are not changed. [Table 15] Pigment obtained in Synthesis Example 2: Pigment (II) 4.0 parts of the pigment obtained in Synthesis Example 3: Pigment (I) 1.0 part of glycerin 5.0 part of urea 5.0 part of N-methyl-2-pyrrolidone 4.0 part Isopropyl alcohol 3.0 parts butyl carbitol 2.0 parts of surfactants 0.1 parts (trade name Surfynol 1〇4, manufactured by Yuxin Chemical Co., Ltd.) 72 201005048 Water + sodium hydroxide 75.9 parts total 100.0 parts [Comparative Examples 1 to 3] The inks (I) and (II) were used as the inks to be compared, and the ink compositions were prepared by mixing the components described in the following Tables 16, 17, and 18, and filtered using a membrane filter of 0.45. Thereby, a comparative ink for inkjet is obtained. In the water system, ion-exchanged water was used in the same manner as in the first embodiment. Further, the pH of the ink composition was adjusted to pH = 8 to 10 by using a 0.1% aqueous solution of sodium hydroxide, and water was added to make the total amount 1 Backup. The preparation of the ink using only the dye (II) obtained in Synthesis Example 1 as the dye was used as Comparative Example 1, and the preparation of the ink using only the dye (Π) obtained in Synthesis Example 2 was used as Comparative Example 2, only The preparation of the ink using the pigment (I) obtained in Synthesis Example 3 was designated as Comparative Example 3.

[表 16] (比較例1) 合成例1中所獲得之色素：色素（II) 3.5份甘油 5.0份尿素 5.0份 N-甲基-2-〃比洛烧嗣 4.0份異丙醇 3.0份丁基卡必醇 2.0份界面活性劑 0.1份 (商品名SurfynollO4，曰信化學公司製造）水+氣氧化納 77.4 份共計 100.0 份 73 201005048 [表 17] (比較例2) 合成例2中所獲得之色素：色素（II) 3.5份甘油 5.0份尿素 5.0份 N-曱基-2-°比略烧酮 4_0份異丙醇 3.0份丁基卡必醇 2.0份界面活性劑〇·1份 (商品名Surfynoll04，曰信化學公司製造）水+氫氧化鈉 77.4份共計 100.0份(Comparative Example 1) Pigment obtained in Synthesis Example 1: Pigment (II) 3.5 parts of glycerin 5.0 parts of urea 5.0 parts of N-methyl-2-indole blister 4.0 parts of isopropyl alcohol 3.0 parts 2.0 parts of kicabi alcohol 2.0 parts of surfactant (trade name: Surfynoll O4, manufactured by Yushin Chemical Co., Ltd.) 77.4 parts of water + gas oxides total 100.0 parts 73 201005048 [Table 17] (Comparative Example 2) The obtained in Synthesis Example 2 Pigment: Pigment (II) 3.5 parts Glycerin 5.0 parts Urea 5.0 parts N-Mercapto-2-° ratio of ketolone 4_0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 〇·1 part (trade name Surfynoll04, manufactured by Yuxin Chemical Co., Ltd.) 77.4 parts of water + sodium hydroxide total 100.0 parts

[表 18] (比較例3 ) 合成例3中所獲得之色素：色素（1) 3.5份甘油 5.0份尿素 5.0份 N-曱基-2-0比略炫^ 4.0份異丙酵 3.0份丁基卡必醇 2.0份界面活性劑 0.1份 (商品名Surfynol 104，日信化學公司製造）水+氫氧化鈉 - 77.4 份共計 100.0 份 [比較例4][Comparative Example 3] Pigment obtained in Synthesis Example 3: Pigment (1) 3.5 parts of glycerin 5.0 parts of urea 5.0 parts of N-mercapto-2-0 ratio slightly dazzling ^ 4.0 parts of isopropanate 3.0 parts 2.0 parts of kicabi alcohol surfactant (trade name Surfynol 104, manufactured by Nissin Chemical Co., Ltd.) water + sodium hydroxide - 77.4 parts total 100.0 parts [Comparative Example 4]

製備揭示於專利文獻1之實施例3 -2的墨水來作為比較例4。此墨水除了 3種色素成分的調配比率不同以外，與各實施例具有同樣的組成。另外，水是使用離子交換水，墨水組成物之pH值係利用氫氧化鈉而調整為8〜1〇，並利用0,45 " m之薄膜過濾器來進行過濾。將此墨水之製備作為比較例4。再者，比較例4是調配了與色素（π)不同之 2種色素與合成例3中所獲得之色素（！）的3種色素而成的黑色墨水’專利文獻i之合成例4所獲得之化合物，係 201005048 與本發明中的合成例3之化合物相同。比較例4之墨水組成係顯示於下述表19。表1 9中，「專利文獻1之實施例2-6所獲得之色素」及「專利文獻1之合成例1所獲得之色素」的結構式，分別是由下述式（29 ) 及（30)來表示。 [化學式29]The ink disclosed in Example 3-2 of Patent Document 1 was prepared as Comparative Example 4. This ink has the same composition as each of the examples except that the blending ratios of the three kinds of pigment components are different. Further, water was ion-exchanged water, and the pH of the ink composition was adjusted to 8 to 1 Torr by using sodium hydroxide, and filtered using a membrane filter of 0, 45 " m. This ink was prepared as Comparative Example 4. In addition, Comparative Example 4 is a black ink obtained by mixing three kinds of dyes different from the dye (π) and the dye (!) obtained in Synthesis Example 3, which is obtained in Synthesis Example 4 of Patent Document i. The compound, 201005048, is the same as the compound of Synthesis Example 3 in the present invention. The ink composition of Comparative Example 4 is shown in Table 19 below. In Table 19, the structural formulas of "pigments obtained in Examples 2 to 6 of Patent Document 1" and "pigments obtained in Synthesis Example 1 of Patent Document 1" are respectively represented by the following formulas (29) and (30). )To represent. [Chemical Formula 29]

[化學式30][Chemical Formula 30]

[表 19] (比較例4) 專利文獻1之實施例2-6所獲得之色素 1.3份專利文獻1之合成例1中所獲得之色素 2.35份專利文獻1之合成例4中所獲得之色素：色素（I) 1.35份甘油 5.0份尿素 5.0份 N-曱基-2-吡咯烷酮 4.0份異丙醇 3.0份丁基卡必醇 2.0份界面活性劑 0.1份 (商品名Surfynol 104，日信化學公司製造）水+氫氧化鈉 75.9份共計 100.0份 75 201005048 [(B )喷墨印刷] 使用上述中所獲得之墨水，利用Canon公司製造之喷墨印表機，商品名為PIXUS iP4100，在Canon公司製造之商品名 Professional Photo Paper PR-1 〇1 (喷墨專用紙）也就是資訊傳遞片材上進行喷墨記錄。於印刷時，以數階段之灰階獲得反射濃度的方式製作圖像圖案’獲得濃黑色〜淡灰色印刷物。 [(C)記錄圖像之評價] 使用實施例卜2、以及比較例卜4之墨水而獲得之各印刷圖像’分別針對对光性以及耐臭氧氣體性，對試賴前後之圖像的黑色之色差ΔΕ進行評價。再者，針對耐済性試驗’是以最小單…，5 _之正方形所構成的核對花樣來進行印刷，並觀察是否有自印刷部分向未印刷部分的色素滲出。針對耐光性及耐臭氧性，印㈣❹ GRETAG MACBETH公司製造之商品名為¥价色機來進行’對試驗前之印刷圖像之反射濃度.加值在Η 〜！.6之範圍内的灰階部分進行測色而測定。再者算反射濃度Dk值時，是以mN作 ° 产。馮濃度基準，並將視角設作2 試驗結果示於表2 〇中。具體的試驗方法如下。 76 201005048 1) 耐臭氧氣體性試驗使用Suga試驗機公司製造的商品名為臭氧耐候試驗機（Ozone Weatherometer )，將各印刷圖像於臭氧濃度為 10 ppm、濕度為60%RH、溫度為24°C之條件下放置24小時。對於分別於臭氧暴露前及暴露後之各印刷圖像，測定 CIE之L*、a*、b*，並使用下述式來計算色差ΔΕ。於 . 測定L *、a *、b *時’光源是使用D65，並將視角設作2 度。再者，下述計算式中，AL*、Aa*、及，意思參分別為暴露前後之L*、a*、b*的差。 ΔΕ= ( Δ L* 2+ Δ a* 2+ Δ b* 2) 1/2 試驗結果係根據以下基準進行評價t評價結果顯示於下述表20 〇〇：△ E小於10 △ : △ E為10以上、小於20 X : △ E為20以上 2) 耐光性試驗，使用SuSa試驗機（股）公司製造的商品名為低溫氙耐 • 候試驗機XL75，於照度為萬Lux、濕度為6〇%RH、溫度為24°C之條件，對上述各印刷圖像進行168小時之照射。對於分別於氙氣光之暴露前與暴露後的各印刷圖像，測定CIE之L*、a*、b*，並使用下述式來計算色差ΔΕ。於測定L*、a氺、b*時，光源是使用D65，並將視角設作2度。再者’下述計算式中，al*、△ a *、及△ b *，意思分別.為暴露前後之 L *、a *、，七*的差〇 77 201005048 1/2 。評價結果.顯.示於 △E ( △ L* 2+ △ a* 2+ △ b* 試驗結果係根據以下基準進行評價下述表20。、〇.△ E小於 △ . ΔΕ為10以上、小於2〇 x : Δ E為20以上 3)耐濕性試驗，用二和科學（股）公司製造之商品…_( c am er 400的恆溫怪濕器，於溫度為24°c、相為8〇%RH之條件，對上述各印刷圖像進行7日之保存^ 試驗後，以目視判斷印刷物的滲墨，全無滲墨者評價為〇，稍有滲墨者評價為X。評價結果顯示於下述表20。 [表 20] 實施例1 耐夷氧氣想性〇實施例2 〇比較例1 Δ 比較例2 〇比較例3 〇比較例4 X 4)色調評價耐光性〇〇〇〇 Δ 〇[Comparative Example 4] The pigment obtained in Example 2-6 of Patent Document 1 is 1.3 parts of the pigment obtained in Synthesis Example 1 of Patent Document 1, 2.35 parts of the pigment obtained in Synthesis Example 4 of Patent Document 1. : Pigment (I) 1.35 parts Glycerin 5.0 parts Urea 5.0 parts N-Mercapto-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (trade name Surfynol 104, Nissin Chemical Co., Ltd. Manufacture) Water + sodium hydroxide 75.9 parts Total 100.0 parts 75 201005048 [(B ) Inkjet printing] Using the ink obtained in the above, using the inkjet printer manufactured by Canon, the trade name is PIXUS iP4100, in Canon The manufactured product name Professional Photo Paper PR-1 〇1 (inkjet paper) is the inkjet recording on the information transfer sheet. At the time of printing, the image pattern was produced in such a manner that the reflection density was obtained in several stages of gray scales to obtain a rich black to light gray printed matter. [(C) Evaluation of Recorded Image] Each of the printed images obtained by using the ink of Example 2 and Comparative Example 4's for the optical property and the ozone-resistant gas property, respectively, for the image before and after the test The color difference ΔΕ of black was evaluated. Further, the tamper resistance test was carried out by printing a check pattern composed of a square of a minimum of ..., 5 _, and observing whether or not there was a bleeding from the printed portion to the unprinted portion. For light resistance and ozone resistance, the printed product of the (4) ❹ GRETAG MACBETH company is called the ¥ price machine to carry out the reflection density of the printed image before the test. The added value is Η ~! The gray scale portion within the range of .6 was measured by colorimetry. In addition, when the reflection concentration Dk is calculated, it is produced by mN. The von concentration benchmark and the viewing angle are set as 2 test results are shown in Table 2. The specific test method is as follows. 76 201005048 1) The ozone gas resistance test uses the Ozone Weatherometer manufactured by Suga Test Machine Co., Ltd., and each printed image has an ozone concentration of 10 ppm, a humidity of 60% RH, and a temperature of 24°. Place under conditions of C for 24 hours. The L*, a*, and b* of the CIE were measured for each of the printed images before and after the ozone exposure, and the color difference ΔΕ was calculated using the following formula. When measuring L*, a*, b*, the light source uses D65 and the viewing angle is set to 2 degrees. Further, in the following calculation formulas, AL*, Aa*, and meaning parameters are differences between L*, a*, and b* before and after exposure, respectively. ΔΕ= ( Δ L* 2+ Δ a* 2+ Δ b* 2) 1/2 The test results are evaluated according to the following criteria. The evaluation results are shown in Table 20 below: △ E is less than 10 △ : △ E is 10 or more, less than 20 X : △ E is 20 or more 2) Light resistance test, using the product name of the SuSa test machine (share) company, the low temperature 氙 resistance tester XL75, the illuminance is 10,000 Lux, the humidity is 6〇 Each of the above-mentioned printed images was irradiated for 168 hours under the conditions of %RH and a temperature of 24 °C. The L*, a*, and b* of the CIE were measured for each of the printed images before and after the exposure of the xenon light, and the color difference ΔΕ was calculated using the following formula. For the measurement of L*, a氺, b*, the light source is D65 and the viewing angle is set to 2 degrees. Further, in the following calculation formulas, al*, Δa*, and Δb* are meanings respectively, which are the difference of L*, a*, and seven* before and after the exposure 〇 77 201005048 1/2 . The evaluation results are shown in ΔE ( △ L* 2+ Δ a* 2+ Δ b* The test results are evaluated according to the following criteria. Table 20, 〇.△ E is less than Δ. ΔΕ is 10 or more, less than 2〇x : Δ E is 20 or more 3) Moisture resistance test, using the products manufactured by Erhe Science Co., Ltd...._(C am er 400 thermostat, at a temperature of 24 ° C, phase 8条件%RH conditions, after the 7-day storage test of each of the above-mentioned printed images, the ink bleed of the printed matter was visually judged, and the bleeder was evaluated as 〇, and the slightly bleeder was evaluated as X. The evaluation result was displayed. In the following Table 20. [Table 20] Example 1 Oxygen-resistant oxygen 〇 Example 2 〇 Comparative Example 1 Δ Comparative Example 2 〇 Comparative Example 3 〇 Comparative Example 4 X 4) Color tone evaluation Light resistance 〇〇〇〇 Δ 〇

耐濕性〇〇〇〇〇〇作為印刷物的顏色評價，係測定高濃度部分與低濃度部分兩者的彩度c *。再者，用於此評價的印刷物，係如同上述’使用以數階段之灰階獲得反射濃度的方式來印刷的圖像圖案，並藉由明度L *之範圍，來區分高濃度部分與低?辰度部分.。亦即，係分別顯示圖像圖案的部分，.其中. 高濃度部分的明度L*之範圍是4.0〜10.0，低濃度部分的 78 201005048 明度L*之範圍是50·0〜60_0。作為無彩色之黑色，c*越接近〇越良好，所以藉以下的判定基準來評價黑色的色調。再者’彩度C氺之值是測定CIE之a*、，並使用下述式來計算。於測定a*、b*時，光源是使用d65，視角是設作2度。再者，由於比較例3之墨水為褐色而明顯並非黑色，所以並未進行此評價》 C*= (a*2+b*2) 1/2 參試驗結果係根據以下基準進行評價。評價結果顯示於下述表21 〇〇：C *小於15 △ : C* 為 15以上、小於20 X : C * 為 20以上 [表 21] 高濃度低濃度實施例1 〇〇實施例2 〇〇比較例1 X X 比較例2 X X 比較例4 〇〇參由表20之結果可明顯得知，比較例4於耐臭氧氣毙方面，是在全部的實施例及比較例中最差者。另外，例1及3分別於耐臭氧氣體性或耐光性方面劣於各^ 例。進而可知’比較例2於耐臭氧氣體性、耐光性、雨性方面，具有與各實施例同等之良好的堅牢性。另一方由表21之結果可明顯得知，顯示了較為良好的堅牢性: 79 201005048 較例1及2,於色調方面其彩度極其高於各實施例，就此點而言其顯示了劣於各實施例的結果。本案發明之各實施例的墨水，在高濃度部分及低濃度部分的兩者中’其彩度C *低’是良好的黑色色調。進而，在圖像堅牢性方面，在耐臭氧氣體性、_光性、及对濕性之任一者中，亦均顯示極其良好的結果。再者如同上述，雖然由於比較例2以目視即呈現明顯的褐色’而未進行色㈣價’但針對堅牢性料以進行試驗。然、而，其耐光性試驗後的色差ΔΕ為1G以上、小於 2〇而評價為「△」，是劣於各實施例者。根據以上結果可知，相較於僅由色素（π)構成之比較例1及比較例2的墨水，含有色素⑴及色素⑻之兩者的各實施例的墨水，色調良好’在獲得所需之黑色色調方面明顯較為優異。另外可知， © 比較例4，雖然調配色素（Π)以外之色素於色素（I)的可獲仔所需的黑色色調，但在圖像堅牢性方面，則以各實施例的墨水較為優異。由以上結果可知’利用本發明之墨水而獲得之印刷匿像的堅牢度極其優異，特別在對喷墨印刷圖像所要求之各種堅牢性、特別是耐臭氧氣體性、财光性、及耐濕性方面極其優異’無論是高濃度或低濃度均呈現良好的里色色調。 … 80 201005048 [產業上之可利用性] 本發明之墨水組成物，適合用作喷墨記錄用、書寫用具用黑色墨水液。【圖式簡單說明】無【主要元件符號說明】 ❹ 無 81Moisture resistance 〇〇〇〇〇〇 As the color evaluation of the printed matter, the chroma c* of both the high concentration portion and the low concentration portion was measured. Further, the printed matter used for this evaluation is as described above using the image pattern printed in such a manner that the reflection density is obtained in a plurality of stages of gray scale, and the high density portion is distinguished by the range of the lightness L*. Chendu part. That is, the portions of the image pattern are respectively displayed, wherein the range of the brightness L* of the high concentration portion is 4.0 to 10.0, and the range of the low density portion 78 201005048 brightness L* is 50·0 to 60_0. As the achromatic black, the closer c* is to the better, the darker color is evaluated by the following criterion. Further, the value of the chroma C is the a* of the CIE, and is calculated using the following formula. For the measurement of a*, b*, the light source is d65 and the angle of view is set to 2 degrees. Further, since the ink of Comparative Example 3 was brown and was not black, it was not evaluated. C*=(a*2+b*2) 1/2 The test results were evaluated based on the following criteria. The evaluation results are shown in the following Table 21: C: C * is less than 15 Δ : C* is 15 or more, and less than 20 X : C * is 20 or more [Table 21] High concentration and low concentration Example 1 〇〇 Example 2 〇〇 Comparative Example 1 XX Comparative Example 2 XX Comparative Example 4 From the results of Table 20, it is apparent that Comparative Example 4 is the worst in all of the examples and comparative examples in terms of ozone gas repellency. Further, Examples 1 and 3 are inferior to each of the examples in terms of ozone gas resistance or light resistance. Further, Comparative Example 2 has excellent fastness equivalent to that of the respective examples in terms of ozone gas resistance, light resistance, and rain resistance. The other party is clearly known from the results of Table 21, showing a relatively good fastness: 79 201005048 Compared to Examples 1 and 2, the chroma in terms of hue is extremely higher than the examples, and in this respect it shows inferiority The results of the various examples. The ink of each of the embodiments of the present invention has a good black hue in both of the high concentration portion and the low concentration portion. Further, in terms of image fastness, extremely excellent results were exhibited in any of ozone gas resistance, light resistance, and wetness. Further, as described above, although Comparative Example 2 showed a clear brown color by visual observation and did not carry out a color (four) price, it was tested for a fast material. However, the color difference ΔΕ after the light resistance test was 1 G or more and less than 2 Å, and was evaluated as "Δ", which was inferior to the examples. According to the above results, it is understood that the inks of the respective examples including the dye (1) and the dye (8) have good color tone compared to the inks of Comparative Example 1 and Comparative Example 2 which are composed only of the dye (π). The black hue is obviously superior. Further, in Comparative Example 4, the pigments other than the pigment (Π) were blended with the black color tone required for the pigment (I), but the ink of each of the examples was excellent in terms of image fastness. From the above results, it is understood that the fastness of the printed image obtained by using the ink of the present invention is extremely excellent, particularly in various fastnesses required for inkjet printed images, particularly ozone gas resistance, richness, and resistance. Extremely excellent in wetness', whether it is high or low, it gives a good color tone. 80 201005048 [Industrial Applicability] The ink composition of the present invention is suitably used as a black ink liquid for inkjet recording or writing. [Simple description of the diagram] None [Key component symbol description] ❹ No 81

Claims

201005048 VII. Patent application scope: 1. An ink composition containing _·(I) or a salt thereof; and an isomer of the following formula (2), or a salt thereof, by the following formula (1) The pigment (II) shown by the pigment shown or its mutual transformation [Chemical Formula 1]

(in equation (1),

Ra represents a hydrogen atom; a hydroxyl group; a carboxyl group; a C1 to C4 alkyl group which may be substituted by a hydroxyl group or a C1 to C4 alkoxy group; a C1 to C4 alkoxy group which may be substituted by a hydroxyl group or a C1 to C4 alkoxy group; Or a C1 to C4 alkoxy group substituted by a C1 to C4 alkylamino group; a carboxyl group of a C1 to C5 alkyl group; a bis(carboxyl C~C5 alkyl)amino group; which may be substituted by a hydroxyl group or a C1 to C4 alkoxy group. a C1-C4 alkylalkylamino group; a phenylamino group which may be substituted with a carboxyl group, a sulfo group or an amine group; a sulfo group; a halogen atom; or a gland group, X represents an aliphatic amine group having a carboxyl group or a sulfo group), [Chemical Formula 2]

(In the formula (2), 82 201005048 R represents a carboxyl group, an unsubstituted or carboxyl group-substituted c丨~C4 alkyl group, or an unsubstituted or reductively substituted stupid group, and R2 is a cyano group or an amine formamidine. a group or a carboxyl group, and R and R are independently a hydrogen atom, a gas atom sulfo group, an unsubstituted C1 to C4 alkyl group, or an unsubstituted C1 to C4 alkoxy group, and a ring substituted by R5 to R7. The ring shown by the dotted line is a stupid ring when it is not present, and is a naphthalene ring in the presence of a ring shown by a broken line, and R5 to R7 each independently represent a hydrogen atom; a gas atom; a transbasic group; a contiguous group; Alkylamino group; unsubstituted ^ to a pyridyl group; unsubstituted, or (d) group, unsubstituted ci~c4 alkoxy group, syllabic C1~C4 alkoxy group, exact base, or county Substituted C1~C4 morphoxy; unsubstituted, or substituted by a radical, a contiguous group, or a succinyl group; or a C1~' C4 alkylamino group; unsubstituted or substituted by a benzyl or a thiol group Cl~C4 alkylamino group; to get , 未经, unsubstituted, or substituted by hydroxyl, sulfo, or carboxyl group, n, -C1~C4 ureidourea; unsubstituted Or a phenylamine group substituted by a C1~C4 group, a cis group, a contiguous group or a hydrazine group; an unsubstituted or a benzene ring via a gas atom, an unsubstituted group, A phenyl, anthracene or a thiol-substituted phenylamino group; or unsubstituted, or a benzene ring via a chlorine atom, an unsubstituted C1 to C4 group, a stone base, a true, a +8 丨, a soil Or a phenyl-terminated amino group substituted with a benzyl group, a ring of m substituted by benzene is a benzene coat when it is not present, and a naphthalene ring in the presence of a ring shown by a dotted line, and R to R. independently represent a hydrogen atom. · a chlorine atom; a hydroxyl group; a sulfo group, an amine group only, an amine group; an unsubstituted alkyl group; 83 201005048 unsubstituted, or a hydroxyl group, an unsubstituted C1 to C4 alkoxy group, a hydroxy C1 - C4 alkoxy group, a sulfo group, or a carboxy group substituted with an alkoxy group; a C1 to C4 alkylthio group substituted with a hydroxyl group, a sulfo group, or a carboxyl group; unsubstituted, or via a hydroxyl group, a sulfo group, Or a carboxy-substituted mono- or di-C1-C4 alkylamino group, unsubstituted or substituted by a hydroxy or carboxy group C1 to C4 alkylcarbonylamine Unsubstituted, or substituted with a hydroxyl group, a sulfo group, or a carboxyl group, N,_cl to C4 alkylureido; unsubstituted, or a cycloalkyl group via a chlorine atom, an unsubstituted φ C1 to C4 alkyl group, a nitro group a sulfo group, or a carboxy-substituted phenylamino group; an unsubstituted benzoylamine substituted by a benzene ring via a gas atom, an unsubstituted c丨~C4 alkyl group, a terminal group, a sulfo group, or a carboxyl group; a phenylsulfonylamino group substituted with a phenyl ring via a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group, or a carboxyl group, the group A being unsubstituted or having The 2-naphthylthiazolyl group of the substituent may have a selected from the group consisting of: a gas atom; a sulfo group; a nitro group; a mercapto group; an amine sulfonyl group; Substituted C1~C4 ❹ alkyl; unsubstituted 'C1~C4 alkoxy substituted by hydroxy, Cl~C4 alkoxy, sulfo, or carboxy; unsubstituted, or via hydroxy, sulfo, or Carboxyl-substituted C1~C4 alkylsulfonyl; and unsubstituted, or benzene ring via chlorine atom, unsubstituted C1~C4 alkyl group, supplementary group, continued a substituent in the group consisting of a phenylsulfonyl group substituted with a carboxy group or a carboxy group. 2. The ink composition according to claim 1, wherein all of the pigments contained in the ink composition are the following: a pigment (I) represented by formula (1) or a salt thereof; a pigment (Π) represented by the formula (2) or an ink composition thereof, or an ink composition according to the above item 1, wherein the pigment represented by the above 3) is as described in 3. The patent formula (I) is derived from the following formula ([Chemical Formula 3]

4. The ink composition according to Item 1, wherein the tX is a mono C1 to C5 alkylamino group having a carboxyl group or a sulfo group or two. Alkylamino group. 5. The ink composition of claim 1, wherein X is a sulfoethylamino group. 6. The ink composition according to claim 1, wherein the pigment (Π) is a pigment represented by the following formula (4), [Chemical Formula 4]

85 201005048 (in the meaning of (4), the meaning). Base A, R1 to

It is the same as the formula (2). 7. The pigment (II) is a pigment represented by the ink composition (5) according to the following formula [Chemical Formula 5], wherein the above

The radicals A'R1 to R4 have the same meanings as in the formula (1), and R5 and R7 each independently represent a hydrogen atom; a gas atom; an unsubstituted or a C1 to C4 alkylcarbonylamino group substituted by a hydroxyl group or a carboxyl group; Substituted C1 to C4 alkyl; or, unsubstituted, or C1 to C4 alkoxy substituted by sulfo or hydroxy,

R6 represents a hydrogen atom, and R8 to R1G each independently represent a hydrogen atom; a gas atom; an unsubstituted, or a C1 to C4 alkylcarbonylamino group substituted with a hydroxyl group or a carboxyl group; a sulfo group; a C1 a C4 alkoxy group; a C 1 -C 4 alkyl group; an unsubstituted or C 1 -C 4 alkyl fluorenyl group substituted by a sulfo group; or a C 1 -C 4 alkylthio group substituted by a sulfo group or a slow group; R 9 represents a hydrogen atom). 86 201005048 wherein the ink composition as described in claim 1 is a group represented by the following formula (6), [Chemical Formula 6]

(6) (In the formula (6), R to r4 are each independently selected from: hydrogen atom; gas atom; contig; nitro; hydroxy; sulfonyl; unsubstituted, or hydroxy, unsubstituted a C1-C4 alkoxy group, a sulfo group, or a carboxyl group substituted with a group of a C1 to C4 alkyl group substituted by a hydroxyl group, a sulfo group, or a carboxyl group; 9. The ink composition according to claim 8, wherein Ri is a methyl 'R2 is a cyano group or an aminomethyl group, R3 is a hydrogen atom, R4 is a sulfo group, and R5 is Sulfopropyloxy or sulfobutoxy, R6 is a hydrogen atom, R7 is a hydrogen atom, a gas atom, an ethylamino group, a decyl group, an ethyl group, a methoxy group, an ethoxy group, a sulfopropoxy group Or a benzyloxy group, R8 is a sulfopropylthio group or a sulfobutylthio group, R is a hydrogen atom, and R10 is a hydrogen atom, a chlorine atom, an ethylamino group, a methyl group, an ethyl group, a decyloxy group, An ethoxy group or a contigyl propoxy group, three of rH to rM are a contiguous group, and one is a hydrogen atom. 10. The ink composition of claim i, wherein in the ink 87 20 1005048 The ratio of the pigment (j) or its salt, the pigment (π) or its tautomer, or the total mass of the salt contained in the water composition, the ratio of the pigment (1) or its salt is 10~ 30% by mass, the ratio of the pigment (11) or its tautomer, or the salt thereof is from 7 〇 to 90% by mass. 11. The ink composition according to claim 1, wherein the ink is relative to the ink The total mass of the composition, the pigment (1) or its salt, and the pigment (Π) or its tautomer, or the total mass of the salt contained in the ink composition is 2 to 8 mass. 0. 12. The ink composition as described in the scope of claim 2, which is used for inkjet recording. I3. An inkjet recording method, which will be used as a patent application. An ink composition as described above is used as an ink, and an ink droplet of the ink is ejected in accordance with a recording signal to be recorded on a material to be recorded. -*. Inkjet as described in claim 13 of the patent application The recording method is used to exchange the above-mentioned materials to be recorded, which is a sheet for information transmission. The sneeze recording method described in the ninth patent, wherein the above-mentioned information transmission sheet, and right-A 士交^)A. 八有3 has a porous white inorganic ink 88 201005048 * 16. A ^ _ item The coloring body is colored by the ink composition as described in claims 1 to 12. The coloring of the coloring matter described in item 16 is carried out by 17. Inkjet printer as claimed in the patent application. An ink jet printer is filled with a container containing the ink composition as described in any one of the above-mentioned patents, the first to the twelfth, <RTIgt; 201005048 IV. Designation of Representative Representatives (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None.

5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:

2 201005048 — The matter of the matter, the number of cases is J. Amendment VII. Patent application scope: "-Ink composition, which contains: "(1) or its salt 4 of the following formula (1) 4 by the following formula (7) [Chemical Formula 1] ho3s H〇3s^'N =WH^'N=N''^y^~N=NH^N=N_Q^ (1) Gan (in the formula (1), the hydrogen atom of the formula 'hydroxyl group; carboxyl group; may be substituted by a hydroxyl group or a C1~C4 alkoxy group C1~C4 alkyl group; C1~C4 alkane gas which can be substituted by a base or C1~C4 alkoxy group. Study "^' C1 to C4 alkylamine which can be substituted by a base or C1~C4 alkoxy group ; · · Cl Cl Cl Cl C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C a phenylamino group substituted with a base, a base or an amine group; a sulfo group, a halogen atom; or a urea group, x represents an aliphatic amine group having a rebel & or a contiguous group, [Chemical Formula 2]

(in equation (2), 82